Lithium containing aluminosilicate glasses

ABSTRACT

A glass pharmaceutical package having a glass composition of 68.00 mol % to 81.00 mol % SiO2, from 4.00 mol % to 11.00 mol % Al2O3, from 0.10 mol % to 16.00 mol % Li2O, from 0.10 mol % to 12.00 mol % Na2O, from 0.00 mol % to 5.00 mol % K2O, from 0.10 mol % to 8.00 mol % MgO, from 0.10 mol % to 5.00 mol % CaO, from 0.00 mol % to 0.20 mol % fining agent. The glass pharmaceutical package is delamination resistant, and has class 1 or class 2 chemical durability in acid, base, and water. The glass pharmaceutical package may have a surface compressive stress of at least 350 MPa.

CROSS REFERENCE TO RELATED APPLICATIONS

The present specification is a divisional of U.S. patent applicationSer. No. 15/825,793 filed Nov. 29, 2017, and entitled “LithiumContaining Aluminosilicate Glasses”, which claims priority to U.S.Provisional Application No. 62/428,311 filed on Nov. 30, 2016, andentitled, “Lithium Containing Aluminosilicate Glasses”, each of which isincorporated herein by reference in their entireties.

BACKGROUND Field

The present specification generally relates to lithium containingaluminosilicate glasses. More specifically, the present specification isdirected to lithium containing aluminosilicate glasses that arestrengthened to have an evenly distributed compressive stress profile.

Technical Background

Historically, glass has been used as the preferred material forpackaging pharmaceuticals because of its hermeticity, optical clarity,and excellent chemical durability relative to other materials.Specifically, the glass used in pharmaceutical packaging must haveadequate chemical durability so as to not affect the stability of thepharmaceutical compositions contained therein. Glasses having suitablechemical durability include those glass compositions within the ASTMstandard E438.92 ‘Type IA’ and ‘Type IB’ glass compositions or glasscompositions within the USP <660> Type 1 compositions, which have aproven history of chemical durability. Many aluminosilicate glasses meetthe criteria for chemical durability described above. In addition, thesealuminosilicate glasses may have relatively greater glass transitiontemperatures and elastic modulus when compared to conventionalborosilicate and soda-lime silicate glasses. Some aluminosilicateglasses may be strengthened, such as by an ion exchange process, toincrease the damage resistance of the glass. However, even strengthenedglass can be damaged, particularly by acute or sharp impact. Ininstances where the glass is strengthened, localized variations in thestrengthened layer can be formed that cause the glass to fracture orcrack in unpredictable and numerous ways.

Accordingly, a need exists for aluminosilicate glasses that can bestrengthened, such as by ion exchange, in a controlled manner such thatthe mechanical properties of the strengthened glass are controlled.

SUMMARY

According to an embodiment, a glass pharmaceutical package has a glasscomposition comprising: from greater than or equal to 68.00 mol % toless than or equal to 81.00 mol % SiO₂; from greater than or equal to4.00 mol % to less than or equal to 11.00 mol % Al₂O₃; from greater thanor equal to 0.10 mol % to less than or equal to 16.00 mol % Li₂O; fromgreater than or equal to 0.10 mol % to less than or equal to 12.00 mol %Na₂O; from greater than or equal to 0.00 mol % to less than or equal to5.00 mol % K₂O; from greater than or equal to 0.10 mol % to less than orequal to 8.00 mol % MgO; from greater than or equal to 0.10 mol % toless than or equal to 5.00 mol % CaO; from greater than or equal to 0.00mol % to less than or equal to 0.20 mol % fining agent. The glasspharmaceutical package is delamination resistant, and has class 1 orclass 2 chemical durability in acid, base, and water.

In another embodiment, a glass pharmaceutical package has a glasscomposition comprising: from greater than or equal to 68.00 mol % toless than or equal to 81.00 mol % SiO₂; from greater than or equal to6.10 mol % to less than or equal to 7.00 mol % Al₂O₃; from greater thanor equal to 3.10 mol % to less than or equal to 4.60 mol % Li₂O; fromgreater than or equal to 1.40 mol % to less than or equal to 3.00 mol %Na₂O; from greater than or equal to 0.00 mol % to less than or equal to5.00 mol % K₂O; from greater than or equal to 5.10 mol % to less than orequal to 7.50 mol % MgO; from greater than or equal to 0.10 mol % toless than or equal to 5.00 mol % CaO; from greater than or equal to 0.00mol % to less than or equal to 0.20 mol % fining agent. The glasspharmaceutical package is delamination resistant, the glasspharmaceutical package has class 1 or class 2 chemical durability inacid, base, and water, and the glass pharmaceutical package issubstantially free of B₂O₃, SrO, BaO, and ZrO₂.

Additional features and advantages will be set forth in the detaileddescription which follows, and in part will be readily apparent to thoseskilled in the art from that description or recognized by practicing theembodiments described herein, including the detailed description whichfollows, the claims, as well as the appended drawings.

It is to be understood that both the foregoing general description andthe following detailed description describe various embodiments and areintended to provide an overview or framework for understanding thenature and character of the claimed subject matter. The accompanyingdrawings are included to provide a further understanding of the variousembodiments, and are incorporated into and constitute a part of thisspecification. The drawings illustrate the various embodiments describedherein, and together with the description serve to explain theprinciples and operations of the claimed subject matter.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 schematically depicts a cross section of a glass havingcompressive stress layers on surfaces thereof according to embodimentsdisclosed and described herein;

FIG. 2 is a plot of SCALP data for a compressive stress profile of aglass article according to embodiments disclosed and described herein;

FIG. 3A is a plot of density and molar volume versus Na₂O mol %according to embodiments disclosed and described herein;

FIG. 3B is a plot of SOC versus Na₂O mol % according to embodimentsdisclosed and described herein;

FIG. 3C is a plot of annealing point, strain point, and softening pointversus Na₂O mol % according to embodiments disclosed and describedherein;

FIG. 3D is a plot of CTE versus Na₂O mol % according to embodimentsdisclosed and described herein;

FIG. 3E is a plot of liquidus temperature versus Na₂O mol % according toembodiments disclosed and described herein;

FIG. 3F is a plot of the crystallization tendency measured by DSCaccording to embodiments disclosed and described herein;

FIG. 3G is a plot of Young's modulus, shear modulus, and Poisson's ratioversus Na₂O mol % according to embodiments disclosed and describedherein;

FIG. 4A is a plot of DIN 12116, ISO 695, and ISO 720 results versus Na₂Omol % according to embodiments disclosed and described herein;

FIG. 4B is a plot of ion concentration in ISO 720 solution versus Na₂Omol % according to embodiments disclosed and described herein;

FIG. 4C is a plot of normalized concentrations of leached components inISO 720 solution versus Na₂O mol % according to embodiments disclosedand described herein;

FIG. 5 is a plot of ISO 720 results versus a ratio of(Li₂O+Na₂O+K₂O)/(SiO₂+Al₂O₃) according to embodiments disclosed anddescribed herein;

FIG. 6 is a plot of ISO 720 results versus softening point according toembodiments disclosed and described herein;

FIG. 7A is a plot of CT versus the duration of an ion exchange treatmentaccording to embodiments disclosed and described herein;

FIG. 7B is a plot of CS versus the duration of an ion exchange treatmentaccording to embodiments disclosed and described herein;

FIG. 7C is a plot of DOL_(k) versus the duration of an ion exchangetreatment according to embodiments disclosed and described herein;

FIG. 8A is a plot of CT versus the duration of an ion exchange treatmentaccording to embodiments disclosed and described herein;

FIG. 8B is a plot of CT versus the duration of an ion exchange treatmentaccording to embodiments disclosed and described herein;

FIGS. 9A-9D are plots of stress versus thickness of glass articlesaccording to embodiments disclosed and described herein;

FIG. 10 is a plot of ISO 720 results versus Na₂O mol % according toembodiments disclosed and described herein;

FIGS. 11A-11D are plots of ion concentration in ISO 720 solution versusNa₂O mol % according to embodiments disclosed and described herein;

FIG. 12A is a plot of ion concentration of Si versus dissolution timeaccording to embodiments disclosed and described herein;

FIG. 12B is a plot of dissolution rate of SiO₂ versus Na₂O mol %according to embodiments disclosed and described herein;

FIG. 13 is a picture of a 50×50×1.1 mm thick ion-exchanged part after apoke testing with a sharp WC tip according to embodiments disclosed anddescribed herein;

FIG. 14 is a picture of a 50×50×1.1 mm thick ion-exchanged part after apoke testing with a sharp WC tip according to embodiments disclosed anddescribed herein;

FIG. 15 is a triangular plot showing hydrolytic durability of glassesversus the distribution of alkali metals according to embodimentsdisclosed and described herein; and

FIG. 16 is a triangular plot showing durability of glasses in a baseversus the distribution of alkali metals according to embodimentsdisclosed and described herein.

DETAILED DESCRIPTION

Reference will now be made in detail to lithium containingaluminosilicate glasses according to various embodiments. The chemicaldurability and physical properties of aluminosilicate glasses generallymay be related to the glass composition and structure. According to someembodiments, a glass pharmaceutical package has a glass compositioncomprising: from greater than or equal to 68.00 mol % to less than orequal to 81.00 mol % SiO₂; from greater than or equal to 4.00 mol % toless than or equal to 11.00 mol % Al₂O₃; from greater than or equal to0.10 mol % to less than or equal to 16.00 mol % Li₂O; from greater thanor equal to 0.10 mol % to less than or equal to 12.00 mol % Na₂O; fromgreater than or equal to 0.00 mol % to less than or equal to 5.00 mol %K₂O; from greater than or equal to 0.10 mol % to less than or equal to8.00 mol % MgO; from greater than or equal to 0.10 mol % to less than orequal to 5.00 mol % CaO; from greater than or equal to 0.00 mol % toless than or equal to 0.20 mol % fining agent. The glass pharmaceuticalpackage is delamination resistant, and has class 1 or class 2 chemicaldurability in acid, base, and water. In some embodiments, the glasspharmaceutical package may be substantially free of B₂O₃, SrO, BaO, andZrO₂.

In the embodiments of the glass containers described herein, theconcentration of constituent components (e.g., SiO₂, Al₂O₃, B₂O₃ and thelike) of the glass composition from which the glass containers areformed are specified in mole percent (mol. %) on an oxide basis, unlessotherwise specified.

The term “substantially free,” when used to describe the concentrationand/or absence of a particular constituent component in a glasscomposition, means that the constituent component is not intentionallyadded to the glass composition. However, the glass composition maycontain traces of the constituent component as a contaminant or tramp inamounts of less than 0.05 mol. %.

The term “chemical durability,” as used herein, refers to the ability ofthe glass composition to resist degradation upon exposure to specifiedchemical conditions. Specifically, the chemical durability of the glasscompositions described herein was assessed according to 4 establishedmaterial testing standards: DIN 12116 dated March 2001 and entitled“Testing of glass—Resistance to attack by a boiling aqueous solution ofhydrochloric acid—Method of test and classification”; ISO 695:1991entitled “Glass—Resistance to attack by a boiling aqueous solution ofmixed alkali—Method of test and classification”; ISO 720:1985 entitled“Glass—Hydrolytic resistance of glass grains at 121 degrees C. —Methodof test and classification”; and ISO 719:1985 “Glass—Hydrolyticresistance of glass grains at 98 degrees C. —Method of test andclassification.” Each standard and the classifications within eachstandard are described in further detail herein. Alternatively, thechemical durability of a glass composition may be assessed according toUSP <660> entitled “Surface Glass Test,” and or European Pharmacopeia3.2.1 Test A-surface test, entitled “Glass Containers For PharmaceuticalUse” which assess the durability of the surface of the glass.

The term “softening point,” as used herein, refers to the temperature atwhich the viscosity of the glass composition is 1×10^(7.6) poise.

The term “annealing point,” as used herein, refers to the temperature atwhich the viscosity of the glass composition is 1×10¹³ poise.

The terms “strain point” and “T_(strain)” as used herein, refers to thetemperature at which the viscosity of the glass composition is 3×10¹⁴poise.

The term “CTE,” as used herein, refers to the coefficient of thermalexpansion of the glass composition over a temperature range from aboutroom temperature (RT) to about 300° C.

The presence of various aluminum coordination states contributes to thephysical properties of alkali aluminosilicate glasses by affecting theratio between bridging oxygen and non-bridging oxygen in the glassnetwork. The alkali species in the glass affect the initial leachingbehavior and interdiffusion reactions during glass dissolution. Theformation of gel or hydrated layer and precipitation on the glasssurface during dissolution also generally relates to the glasscomposition. As used herein, the term “glass composition” refers to theglass composition of a glass article, such as, for example, glasspackaging for pharmaceuticals (e.g., a vial, a syringe, and ampoule,etc.)

In addition, alkali aluminosilicate glasses have good ion exchangeability, and chemical strengthening processes have been used to achievehigh strength and high toughness properties in alkali aluminosilicateglasses. For example, sodium aluminosilicate glasses are highly ionexchangeable glasses with high glass formability and quality. Thesubstitution of Al₂O₃ into the silicate glass network increases theinterdiffusivity of monovalent cations during ion exchange. By chemicalstrengthening in a molten salt bath (e.g., KNO₃ and/or NaNO₃), glasseswith high strength, high toughness, and high indentation crackingresistance can be achieved.

Therefore, alkali aluminosilicate glasses with good physical properties,chemical durability, and ion exchange ability have drawn attention forpharmaceutical packaging. Embodiments disclosed and described hereininclude Li-containing aluminosilicate glasses, which have lowerannealing and softening temperatures, lower coefficient of thermalexpansion (CTE) values, and fast ion exchange ability. Through differention exchange processes (e.g., two-step ion exchange or using one or moremixed salt bath(s)), greater central tension (CT), deeper depth of layerpenetration by potassium (DOL_(k)), depth of compression (DOC), and CTvalues that provide favorable breakage patterns can be achieved.However, some aluminosilicate glass compositions with high Li₂O contentstend to crystallize during the reheating and reforming process, and Lications are much more extractable than Na cations, K cations, andalkaline cations during glass dissolution. So, the composition range ofLi-containing aluminosilicate glasses according to some embodiments maybe limited due to the requirement for acceptable Li cation leached intosolution, such as pharmaceutical solutions.

The benefits of adding Li₂O on the physical properties of the glass, thechemical durability of the glass, and ion exchange ability are describedherein. The addition of Li₂O into aluminosilicate glasses decreases thesoftening temperature, decreases the tube drawing and reformingtemperatures, and increases the hydrolytic chemical durability. Withadding a relatively small amount of Li₂O (e.g., from greater than orequal to 2.00 mol % to less than or equal to 4.00 mol %) intoaluminosilicate glasses, the hydrolytic chemical durability is greatlyimproved (e.g., from about 56 to about 54 by ISO 720 as compared to 68in lithium-free glass) before ion exchange. Another benefit of addingLi₂O is the improvement of ion exchange ability. For instance, stressprofile, CT, surface CS, DOC, and DOL_(k) could be varied to a muchlarger degree after ion exchange than in alkali aluminosilicate glassescontaining Na₂O. For Li₂O containing glasses, a greater CT can beachieved in shorter times compared to lithium-free glasses, and the ionexchange process can be made in several steps or by various conditions,so the stress profile can be tailored easily to suit differentapplications for various products.

Described herein are Li containing aluminosilicate glass compositionsaccording to embodiments, physical properties of Li containingaluminosilicate glass compositions according to embodiments, ionexchange ability benefits of Li containing aluminosilicate glasscompositions according to embodiments, and dissolution kinetics of Licontaining aluminosilicate glass compositions according to embodimentsbefore and after ion exchange.

In embodiments of glass compositions described herein, the amount ofconstituent components (e.g., SiO₂, Al₂O₃, Li₂O, and the like) are givenin mole percent (mol %) on an oxide basis, unless otherwise specified.Components of the Li containing aluminosilicate glass compositionaccording to embodiments are discussed individually below. It should beunderstood that any of the variously recited ranges of one component maybe combined with the any of the variously recited ranges for any othercomponent in a single glass composition.

In an exemplary Li containing aluminosilicate glass composition, SiO₂ isthe largest constituent and, as such, SiO₂ is the primary constituent ofthe glass network formed from the glass composition. Pure SiO₂ has arelatively low CTE and is alkali free. However, pure SiO₂ has anextremely high melting point. Accordingly, if the amount of SiO₂ in theglass composition is too high, the formability of the glass compositionmay be diminished as higher amounts of SiO₂ increase the difficulty ofmelting the glass, which, in turn, adversely impacts the formability ofthe glass. In embodiments, the glass composition generally comprisesSiO₂ in an amount from greater than or equal to 68.00% to less than orequal to 81.00 mol %. In some embodiments, the glass compositioncomprises SiO₂ in amounts greater than or equal to 70.00 mol %, greaterthan or equal to 72.00 mol %, greater than or equal to 74.00 mol %,greater than or equal to 76.00 mol %, or greater than or equal to 78.00mol %. In some embodiments, the glass composition comprises SiO₂ inamounts less than or equal to 80.00 mol %, less than or equal to 78.00mol %, less than or equal to 76.00 mol %, less than or equal to 74.00mol %, or less than or equal to 72.00 mol %. In other embodiments, theglass composition comprises SiO₂ in an amount from greater than or equalto 70.00 mol % to less than or equal to 80.00 mol %, such as fromgreater than or equal to 72.00 mol % to less than or equal to 78.00 mol%, or from greater than or equal to 74.00 mol % to less than or equal to76.00 mol %. In yet other embodiments, the glass composition comprisesSiO₂ in an amount from greater than or equal to 74.00 mol % to less thanor equal to 79.00 mol %.

The glass composition of embodiments may further comprise Al₂O₃. Al₂O₃may also serve as a glass network former, similar to SiO₂. Al₂O₃ mayincrease the viscosity of the glass composition due to its tetrahedralcoordination in a glass melt formed from a properly designed glasscomposition, decreasing the formability of the glass composition whenthe amount of Al₂O₃ is too high. However, when the amount of Al₂O₃ isbalanced against the amount of SiO₂ and the amount of alkali oxides inthe glass composition, Al₂O₃ can reduce the liquidus temperature of theglass melt, thereby enhancing the liquidus viscosity and improving thecompatibility of the glass composition with certain forming processes,such as molding processes. In embodiments, the glass compositiongenerally comprises Al₂O₃ in an amount from greater than or equal to4.00 mol % to less than or equal to 11.00 mol %. In some embodiments,the glass composition comprises Al₂O₃ in amounts greater than or equalto 5.00 mol %, greater than or equal to 6.00 mol %, greater than orequal to 7.00 mol %, greater than or equal to 8.00 mol %, greater thanor equal to 9.00 mol %, or greater than or equal to 10.00 mol %. In someembodiments, the glass composition comprises Al₂O₃ in amounts less thanor equal to 10.00 mol %, less than or equal to 9.00 mol %, less than orequal to 8.00 mol %, less than or equal to 7.00 mol %, less than orequal to 6.00 mol %, or less than or equal to 5.00 mol %. In otherembodiments, the glass composition comprises Al₂O₃ in an amount fromgreater than or equal to 5.00 mol % to less than or equal to 10.00 mol%, such as from greater than or equal to 6.00 mol % to less than orequal to 9.00 mol %, or from greater than or equal to 7.00 mol % to lessthan or equal to 8.00 mol %. In yet other embodiments, the glasscomposition comprises Al₂O₃ in an amount from greater than or equal to5.00 mol % to less than or equal to 11.00 mol %.

The effects of Li₂O in the glass composition are discussed above anddiscussed in further detail below. In embodiments, the glass compositiongenerally comprises Li₂O in an amount from greater than or equal to 0.10mol % to less than or equal to 16.00 mol %. In some embodiments, theglass composition comprises Li₂O in amounts greater than or equal to0.50 mol %, greater than or equal to 1.00 mol %, greater than or equalto 1.50 mol %, greater than or equal to 2.00 mol %, greater than orequal to 2.50 mol %, greater than or equal to 3.00 mol %, greater thanor equal to 3.50 mol %, greater than or equal to 4.00 mol %, greaterthan or equal to 4.50 mol %, greater than or equal to 5.00 mol %,greater than or equal to 5.50 mol %, greater than or equal to 6.00 mol%, greater than or equal to 6.50 mol %, greater than or equal to 7.00mol %, greater than or equal to 7.50 mol %, greater than or equal to8.00 mol %, greater than or equal to 8.50 mol %, greater than or equalto 9.00 mol %, greater than or equal to 9.50 mol %, greater than orequal to 10.00 mol %, greater than or equal to 10.50 mol %, greater thanor equal to 11.00 mol %, greater than or equal to 11.50 mol %, greaterthan or equal to 12.00 mol %, greater than or equal to 12.50 mol %,greater than or equal to 13.00 mol %, greater than or equal to 13.50 mol%, greater than or equal to 14.00 mol %, greater than or equal to 14.50mol %, greater than or equal to 15.00 mol %, or greater than or equal to15.50 mol %. In some embodiments, the glass composition comprises Li₂Oin amounts less than or equal to 0.50 mol %, less than or equal to 1.00mol %, less than or equal to 1.50 mol %, less than or equal to 2.00 mol%, less than or equal to 2.50 mol %, less than or equal to 3.00 mol %,less than or equal to 3.50 mol %, less than or equal to 4.00 mol %, lessthan or equal to 4.50 mol %, less than or equal to 5.00 mol %, less thanor equal to 5.50 mol %, less than or equal to 6.00 mol %, less than orequal to 6.50 mol %, less than or equal to 7.00 mol %, less than orequal to 7.50 mol %, less than or equal to 8.00 mol %, less than orequal to 8.50 mol %, less than or equal to 9.00 mol %, less than orequal to 9.50 mol %, less than or equal to 10.00 mol %, less than orequal to 10.50 mol %, less than or equal to 11.00 mol %, less than orequal to 11.50 mol %, less than or equal to 12.00 mol %, less than orequal to 12.50 mol %, less than or equal to 13.00 mol %, less than orequal to 13.50 mol %, less than or equal to 14.00 mol %, less than orequal to 14.50 mol %, less than or equal to 15.00 mol %, or less than orequal to 15.50 mol %. In other embodiments, the glass compositioncomprises Li₂O in an amount from greater than or equal to 0.50 mol % toless than or equal to 15.50 mol %, such as from greater than or equal to1.00 mol % to less than or equal to 15.00 mol %, from greater than orequal to 1.50 mol % to less than or equal to 14.50 mol %, from greaterthan or equal to 2.00 mol % to less than or equal to 14.00 mol %, fromgreater than or equal to 2.50 mol % to less than or equal to 13.50 mol%, from greater than or equal to 3.00 mol % to less than or equal to13.00 mol %, from greater than or equal to 3.50 mol % to less than orequal to 12.50 mol %, from greater than or equal to 4.00 mol % to lessthan or equal to 12.00 mol %, from greater than or equal to 4.50 mol %to less than or equal to 11.50 mol %, from greater than or equal to 5.00mol % to less than or equal to 11.00 mol %, from greater than or equalto 5.50 mol % to less than or equal to 10.50 mol %, from greater than orequal to 6.00 mol % to less than or equal to 10.00 mol %, from greaterthan or equal to 6.50 mol % to less than or equal to 9.50 mol %, fromgreater than or equal to 7.00 mol % to less than or equal to 9.00 mol %,or from greater than or equal to 7.50 mol % to less than or equal to8.50 mol %. In yet other embodiments, the glass composition comprisesLi₂O in an amount from greater than or equal to 0.10 mol % to less thanor equal to 14.00 mol %.

According to embodiments, the glass composition may also comprise alkalimetal oxides other than Li₂O, such as, for example, Na₂O and K₂O. Na₂Oaids in the ion exchange ability of the glass composition, increases themelting point of the glass composition, and improves formability of theglass composition. However, if too much Na₂O is added to the glasscomposition, the CTE may be too high, and the melting point may be toohigh. In embodiments, the glass composition generally comprises Na₂O inan amount from greater than or equal to 0.10 mol % to less than or equalto 12.00 mol %. In some embodiments, the glass composition comprisesNa₂O in amounts greater than or equal to 0.50 mol %, greater than orequal to 1.00 mol %, greater than or equal to 1.50 mol %, greater thanor equal to 2.00 mol %, greater than or equal to 2.50 mol %, greaterthan or equal to 3.00 mol %, greater than or equal to 3.50 mol %,greater than or equal to 4.00 mol %, greater than or equal to 4.50 mol%, greater than or equal to 5.00 mol %, greater than or equal to 5.50mol %, greater than or equal to 6.00 mol %, greater than or equal to6.50 mol %, greater than or equal to 7.00 mol %, greater than or equalto 7.50 mol %, greater than or equal to 8.00 mol %, greater than orequal to 8.50 mol %, greater than or equal to 9.00 mol %, greater thanor equal to 9.50 mol %, greater than or equal to 10.00 mol %, greaterthan or equal to 10.50 mol %, greater than or equal to 11.00 mol %, orgreater than or equal to 11.50 mol %. In some embodiments, the glasscomposition comprises Na₂O in amounts less than or equal to 0.50 mol %,less than or equal to 1.00 mol %, less than or to 1.50 mol %, less thanor equal to 2.00 mol %, less than or equal to 2.50 mol %, less than orequal to 3.00 mol %, less than or equal to 3.50 mol %, less than orequal to 4.00 mol %, less than or equal to 4.50 mol %, less than orequal to 5.00 mol %, less than or equal to 5.50 mol %, less than orequal to 6.00 mol %, less than or equal to 6.50 mol %, less than orequal to 7.00 mol %, less than or equal to 7.50 mol %, less than orequal to 8.00 mol %, less than or equal to 8.50 mol %, less than orequal to 9.00 mol %, less than or equal to 9.50 mol %, less than orequal to 10.00 mol %, less than or equal to 10.50 mol %, less than orequal to 11.00 mol %, or less than or equal to 11.50 mol %. In otherembodiments, the glass composition comprises Na₂O in an amount fromgreater than or equal to 0.50 mol % to less than or equal to 11.50 mol%, such as from greater than or equal to 1.00 mol % to less than orequal to 11.00 mol %, from greater than or equal to 1.50 mol % to lessthan or equal to 10.50 mol %, from greater than or equal to 2.00 mol %to less than or equal to 10.00 mol %, from greater than or equal to 2.50mol % to less than or equal to 9.50 mol %, from greater than or equal to3.00 mol % to less than or equal to 9.00 mol %, from greater than orequal to 3.50 mol % to less than or equal to 8.50 mol %, from greaterthan or equal to 4.00 mol % to less than or equal to 7.00 mol %, fromgreater than or equal to 4.50 mol % to less than or equal to 6.50 mol %,or from greater than or equal to 5.00 mol % to less than or equal to6.00 mol %. In yet other embodiments, the glass composition comprisesNa₂O in an amount from greater than or equal to 0.10 mol % to less thanor equal to 10.00 mol %.

Like Na₂O, K₂O also promotes ion exchange and increases the DOC of acompressive stress layer. However, adding K₂O in amounts greater thanabout 5.00 mol % may result in the CTE being too high, and the meltingpoint may be too high. In embodiments, the glass composition generallycomprises K₂O in an amount from greater than or equal to 0.00 mol % toless than or equal to 5.00 mol %, or greater than or equal to 0.10 mol %to less than or equal to 5.00 mol %. In some embodiments, the glasscomposition comprises K₂O in amounts greater than or equal to 0.50 mol%, greater than or equal to 1.00 mol %, greater than or equal to 1.50mol %, greater than or equal to 2.00 mol %, greater than or equal to2.50 mol %, greater than or equal to 3.00 mol %, greater than or equalto 3.50 mol %, greater than or equal to 4.00 mol %, or greater than orequal to 4.50 mol %. In some embodiments, the glass compositioncomprises K₂O in amounts less than or equal to 0.50 mol %, less than orequal to 1.00 mol %, less than or equal to 1.50 mol %, less than orequal to 2.00 mol %, less than or equal to 2.50 mol %, less than orequal to 3.00 mol %, less than or equal to 3.50 mol %, less than orequal to 4.00 mol %, or less than or equal to 4.50 mol %. In otherembodiments, the glass composition comprises K₂O in an amount fromgreater than or equal to 0.50 mol % to less than or equal to 4.50 mol %,such as from greater than or equal to 1.00 mol % to less than or equalto 4.00 mol %, from greater than or equal to 1.50 mol % to less than orequal to 3.50 mol %, or from greater than or equal to 2.00 mol % to lessthan or equal to 3.00 mol %. From the above, it should be understoodthat some embodiments do not include K₂O.

MgO lowers the viscosity of a glass, which enhances the formability, thestrain point, the Young's modulus, and may improve the ion exchangeability. However, when MgO is added in amounts greater than about 8.00mol % to the glass composition, the density and the CTE of the glasscomposition increase. In embodiments, the glass composition generallycomprises MgO in an amount from greater than or equal to 0.10 mol % toless than or equal to 8.00 mol %. In some embodiments, the glasscomposition comprises MgO in amounts greater than or equal to 0.50 mol%, greater than or equal to 1.00 mol %, greater than or equal to 1.50mol %, greater than or equal to 2.00 mol %, greater than or equal to2.50 mol %, greater than or equal to 3.00 mol %, greater than or equalto 3.50 mol %, greater than or equal to 4.00 mol %, greater than orequal to 4.50 mol %, greater than or equal to 5.00 mol %, greater thanor equal to 5.50 mol %, greater than or equal to 6.00 mol %, greaterthan or equal to 6.50 mol %, greater than or equal to 7.00 mol %, orgreater than or equal to 7.50 mol %. In some embodiments, the glasscomposition comprises MgO in amounts less than or equal to 0.50 mol %,less than or equal to 1.00 mol %, less than or equal to 1.50 mol %, lessthan or equal to 2.00 mol %, less than or equal to 2.50 mol %, less thanor equal to 3.00 mol %, less than or equal to 3.50 mol %, less than orequal to 4.00 mol %, less than or equal to 4.50 mol % less than or equalto 5.00 mol %, less than or equal to 5.50 mol %, less than or equal to6.00 mol %, less than or equal to 6.50 mol %, less than or equal to 7.00mol %, or less than or equal to 7.50 mol %. In other embodiments, theglass composition comprises MgO in an amount from greater than or equalto 0.50 mol % to less than or equal to 7.50 mol %, such as from greaterthan or equal to 1.00 mol % to less than or equal to 7.00 mol %, fromgreater than or equal to 1.50 mol % to less than or equal to 6.50 mol %,from greater than or equal to 2.00 mol % to less than or equal to 6.00mol %, from greater than or equal to 2.50 mol % to less than or equal to5.50 mol %, from greater than or equal to 3.00 mol % to less than orequal to 5.00 mol %, or from greater than or equal to 3.50 mol % to lessthan or equal to 4.50 mol %.

CaO lowers the viscosity of a glass, which enhances the formability, thestrain point and the Young's modulus. However, when too much CaO isadded to the glass composition, the density and the CTE of the glasscomposition increase, and the ion exchange ability of the glassdecreases. In embodiments, the glass composition generally comprises CaOin an amount from greater than or equal to 0.10 mol % to less than orequal to 5.00 mol %. In some embodiments, the glass compositioncomprises CaO in amounts greater than or equal to 0.50 mol %, greaterthan or equal to 1.00 mol %, greater than or equal to 1.50 mol %,greater than or equal to 2.00 mol %, greater than or equal to 2.50 mol%, greater than or equal to 3.00 mol %, greater than or equal to 3.50mol %, greater than or equal to 4.00 mol %, or greater than or equal to4.50 mol %. In some embodiments, the glass composition comprises CaO inamounts less than or equal to 0.50 mol %, less than or equal to 1.00 mol%, less than or equal to 1.50 mol %, less than or equal to 2.00 mol %,less than or equal to 2.50 mol %, less than or equal to 3.00 mol %, lessthan or equal to 3.50 mol %, less than or equal to 4.00 mol %, or lessthan or equal to 4.50 mol %. In other embodiments, the glass compositioncomprises CaO in an amount from greater than or equal to 0.50 mol % toless than or equal to 4.50 mol %, such as from greater than or equal to1.00 mol % to less than or equal to 4.00 mol %, from greater than orequal to 1.50 mol % to less than or equal to 3.50 mol %, or from greaterthan or equal to 2.00 mol % to less than or equal to 3.00 mol %.

In embodiments, the glass composition may optionally include one or morefining agents. In some embodiments, the fining agents may include, forexample, SnO₂, CeO₂, As₂O₃, Sb₂O₃, Cl⁻, S⁻, F⁻, or Fe₂O₃. In suchembodiments, the fining agent may be present in the glass composition inan amount from greater than or equal to 0.00 mol % to less than or equalto 0.20 mol %, such as from greater than or equal to 0.00 mol % to lessthan or equal to 0.10 mol %, or from greater than or equal to 0.00 mol %to less than or equal to 0.05 mol %. In other embodiments, the finingagent may be present in the glass composition in an amount from greaterthan or equal to 0.05 mol % to less than or equal to 0.20 mol %, such asfrom greater than or equal to 0.05 mol % to less than or equal to 0.10mol %.

In some embodiments the glass compositions may further comprise minoramounts of one or more additional oxides such as, for example, ZnO,TiO₂, ZrO₂, or the like. These components may be added to furtherenhance the chemical durability of the glass composition and/or improveother properties, such as, for example CTE, density, ion exchangeability, and viscosity. In such embodiments, the additional oxides maybe present in the glass composition in an amount from greater than orequal to 0.00 mol % to less than or equal to 0.20 mol %, such as fromgreater than or equal to 0.00 mol % to less than or equal to 0.10 mol %,or from greater than or equal to 0.00 mol % to less than or equal to0.05 mol %. In other embodiments, the additional oxides may be presentin the glass composition in an amount from greater than or equal to 0.05mol % to less than or equal to 0.20 mol %, such as from greater than orequal to 0.05 mol % to less than or equal to 0.10 mol %.

In any embodiment described above, the glass composition may besubstantially free of B₂O₃, BaO, SrO, or combinations thereof. It shouldbe understood that in embodiments the glass composition may besubstantially free of all three of these components, in otherembodiments, the glass composition may be substantially free of anythree of these components, in yet other embodiments, the glasscomposition may be substantially free of any two of these components,and in still other embodiments, the glass composition may besubstantially free of any one of these components. As used herein, theterm “substantially free” means that the component is not added as acomponent of the batch material even though the component may be presentin the final glass in very small amounts as a contaminate, such as lessthan 0.1 mol %.

However, in other embodiments, the glass composition can contain smallamounts of B₂O₃. In such embodiments, B₂O₃ may be present in amountsfrom greater than or equal to 0.5 mol % to less than or equal to 3.0 mol%, such as from greater than or equal to 0.5 mol % to less than or equalto 2.5 mol %, greater than or equal to 0.5 mol % to less than or equalto 2.0 mol %, greater than or equal to 0.5 mol % to less than or equalto 1.5 mol %, or greater than or equal to 0.5 mol % to less than orequal to 1.0 mol %. In some embodiments, the B₂O₃ may be present in theglass composition in amounts from greater than or equal to 1.0 mol % toless than or equal to 3.0 mol %, such as greater than or equal to 1.0mol % to less than or equal to 2.5 mol %, greater than or equal to 1.0mol % to less than or equal to 2.0 mol %, or greater than or equal to1.0 mol % to less than or equal to 1.5 mol %.

In addition to the above, the ratio of total alkali metals to networkforming components (i.e., (Li₂O+Na₂O+K₂O)/(SiO₂+Al₂O₃)) may also beadjusted to increase the hydrolytic durability of the glass composition.In embodiments, the ratio of total alkali metals to network formingcomponents is from greater than or equal to 0.05 to less than or equalto 0.50, such as from greater than or equal to 0.10 to less than orequal to 0.45, from greater than or equal to 0.15 to less than or equalto 0.40, from greater than or equal to 0.20 to less than or equal to0.35, or from greater than or equal to 0.25 to less than or equal to0.30. In other embodiments, the ratio of total alkali metals to networkforming components is from greater than or equal to 0.10 to less than orequal to 0.50, from greater than or equal to 0.15 to less than or equalto 0.50, from greater than or equal to 0.20 to less than or equal to0.50, from greater than or equal to 0.25 to less than or equal to 0.50,from greater than or equal to 0.30 to less than or equal to 0.50, fromgreater than or equal to 0.35 to less than or equal to 0.50, fromgreater than or equal to 0.40 to less than or equal to 0.50, or fromgreater than or equal to 0.45 to less than or equal to 0.50. In yetother embodiments, the ratio of total alkali metals to network formingcomponents is from greater than or equal to 0.05 to less than or equalto 0.45, from greater than or equal to 0.05 to less than or equal to0.40, from greater than or equal to 0.05 to less than or equal to 0.35,from greater than or equal to 0.05 to less than or equal to 0.30, fromgreater than or equal to 0.05 to less than or equal to 0.25, fromgreater than or equal to 0.05 to less than or equal to 0.20, fromgreater than or equal to 0.05 to less than or equal to 0.15, or fromgreater than or equal to 0.05 to less than or equal to 0.10. In stillother embodiments, the ratio of total alkali metals to network formingcomponents is from greater than or equal to 0.05 to less than or equalto 0.15, the ratio of total alkali metals to network forming componentsis from greater than or equal to 0.05 to less than or equal to 0.14, theratio of total alkali metals to network forming components is fromgreater than or equal to 0.05 to less than or equal to 0.13, the ratioof total alkali metals to network forming components is from greaterthan or equal to 0.05 to less than or equal to 0.12, the ratio of totalalkali metals to network forming components is from greater than orequal to 0.05 to less than or equal to 0.11, or the ratio of totalalkali metals to network forming components is from greater than orequal to 0.05 to less than or equal to 0.10.

Further, in embodiments, the glass composition may comprise a ratio ofR₂O:RO from greater than or equal to 0.75 to less than or equal to 4.25,where R₂O is the sum of alkali metal oxides in the glass composition andRO is the sum of alkaline earth metal oxides in the glass composition.In some embodiments, the glass composition may have a R₂O:RO ratiogreater than or equal to 1.00, greater than or equal to 1.25, greaterthan or equal to 1.50, greater than or equal to 1.75, greater than orequal to 2.00, greater than or equal to 2.25, greater than or equal to2.50, greater than or equal to 2.50, greater than or equal to 2.75,greater than or equal to 3.00, greater than or equal to 3.25, greaterthan or equal to 3.50, greater than or equal to 3.75, or greater than orequal to 4.00. In other embodiments, the glass composition may have aR₂O:RO ratio less than or equal to 1.00, less than or equal to 1.25,less than or equal to 1.50, less than or equal to 1.75, less than orequal to 2.00, less than or equal to 2.25, less than or equal to 2.50,less than or equal to 2.50, less than or equal to 2.75, less than orequal to 3.00, less than or equal to 3.25, less than or equal to 3.50,less than or equal to 3.75, or less than or equal to 4.00. In yet otherembodiments, the glass composition may have a R₂O:RO ratio from greaterthan or equal to 1.00 to less than or equal to 4.00, from greater thanor equal to 1.25 to less than or equal to 3.75, from greater than orequal to 1.50 to less than or equal to 3.50, from greater than or equalto 1.75 to less than or equal to 3.25, from greater than or equal to2.00 to less than or equal to 3.00, or from greater than or equal to2.25 to less than or equal to 2.75. In further embodiments, the R₂O:ROratio is from greater than or equal to 0.85 to less than or equal to2.55, such as from greater than or equal to 0.85 to less than or equalto 2.20, or from greater than or equal to 0.95 to less than or equal to2.20.

In embodiments, the glass composition may comprise a Li₂O:R₂O ratio fromgreater than or equal to 0.10 to less than or equal to 1.00. In someembodiments, the Li₂O:R₂O ratio is greater than or equal to 0.15,greater than or equal to 0.20, greater than or equal to 0.25, greaterthan or equal to 0.30, greater than or equal to 0.35, greater than orequal to 0.40, greater than or equal to 0.45, greater than or equal to0.50, greater than or equal to 0.55, greater than or equal to 0.60,greater than or equal to 0.65, greater than or equal to 0.70, greaterthan or equal to 0.75, greater than or equal to 0.80, greater than orequal to 0.85, greater than or equal to 0.90, or greater than or equalto 0.95. In other embodiments, the Li:R₂O ratio is less than or equal to0.15, less than or equal to 0.20, less than or equal to 0.25, less thanor equal to 0.30, less than or equal to 0.35, less than or equal to0.40, less than or equal to 0.45, less than or equal to 0.50, less thanor equal to 0.55, less than or equal to 0.60, less than or equal to0.65, less than or equal to 0.70, less than or equal to 0.75, less thanor equal to 0.80, less than or equal to 0.85, less than or equal to0.90, or less than or equal to 0.95. In yet other embodiments, theLi₂O:R₂O ratio is from greater than or equal to 0.15 to less than orequal to 0.95, from greater than or equal to 0.20 to less than or equalto 0.90, from greater than or equal to 0.25 to less than or equal to0.85, from greater than or equal to 0.30 to less than or equal to 0.80,from greater than or equal to 0.35 to less than or equal to 0.75, fromgreater than or equal to 0.40 to less than or equal to 0.70, fromgreater than or equal to 0.45 to less than or equal to 0.65, or fromgreater than or equal to 0.50 to less than or equal to 0.60. In furtherembodiments, the Li₂O:R₂O ratio is from greater than or equal to 0.55 toless than or equal to 0.85, such as from greater than or equal to 0.60to less than or equal to 0.85, or from greater than or equal to 0.60 toless than or equal to 0.80.

In yet other embodiments, the glass composition may comprise a Li₂O:ROratio from greater than or equal to 0.25 to less than or equal to 3.50.In some embodiments, the Li:RO ratio is greater than or equal to 0.50,greater than or equal to 0.75, greater than or equal to 1.00, greaterthan or equal to 1.25, greater than or equal to 1.50, greater than orequal to 1.75, greater than or equal to 2.00, greater than or equal to2.25, greater than or equal to 2.50, greater than or equal to 2.75,greater than or equal to 3.00, or greater than or equal to 3.25. Inother embodiments, the Li₂O:RO ratio is less than or equal to 0.50, lessthan or equal to 0.75, less than or equal to 1.00, less than or equal to1.25, less than or equal to 1.50, less than or equal to 1.75, less thanor equal to 2.00, less than or equal to 2.25, less than or equal to2.50, less than or equal to 2.75, less than or equal to 3.00, or lessthan or equal to 3.25. In yet other embodiments, the Li₂O:RO ratio isfrom greater than or equal to 0.50 to less than or equal to 3.25, fromgreater than or equal to 0.75 to less than or equal to 3.00, fromgreater than or equal to 1.00 to less than or equal to 2.75, fromgreater than or equal to 1.25 to less than or equal to 2.50, fromgreater than or equal to 1.50 to less than or equal to 2.25, or fromgreater than or equal to 1.75 to less than or equal to 2.00. In furtherembodiments, the Li₂O:RO ratio is from greater than or equal to 0.40 toless than or equal to 2.00, such as from greater than or equal to 0.40to less than or equal to 1.80, or from greater than or equal to 0.45 toless than or equal to 1.80.

The glass composition may, in some embodiments, comprise a Li₂O:Al₂O₃ratio from greater than or equal to 0.10 to less than or equal to 2.75.In some embodiments, the Li₂O:Al₂O₃ ratio is greater than or equal to0.25, greater than or equal to 0.50, greater than or equal to 0.75,greater than or equal to 1.00, greater than or equal to 1.25, greaterthan or equal to 1.50, greater than or equal to 1.75, greater than orequal to 2.00, greater than or equal to 2.25, or greater than or equalto 2.50. In other embodiments, the Li₂O:Al₂O₃ ratio is less than orequal to 0.25, less than or equal to 0.50, less than or equal to 0.75,less than or equal to 1.00, less than or equal to 1.25, less than orequal to 1.50, less than or equal to 1.75, less than or equal to 2.00,less than or equal to 2.25, or less than or equal to 2.50. In yet otherembodiments, the Li₂O:Al₂O₃ ratio is from greater than or equal to 0.25to less than or equal to 2.50, from greater than or equal to 0.50 toless than or equal to 2.25, from greater than or equal to 0.75 to lessthan or equal to 2.00, from greater than or equal to 1.00 to less thanor equal to 1.75, or from greater than or equal to 1.25 to less than orequal to 1.50. In further embodiments, the Li₂O:Al₂O₃ ratio is fromgreater than or equal to 0.55 to less than or equal to 2.00, such asfrom greater than or equal to 0.55 to less than or equal to 1.50, orfrom greater than or equal to 0.60 to less than or equal to 1.50.

In yet other embodiments, the glass composition may comprise a R₂O:Al₂O₃ratio from greater than or equal to 0.9 to less than or equal to 2.0. Insome embodiments, the R₂O:Al₂O₃ ratio is greater than or equal to 1.0,greater than or equal to 1.1, greater than or equal to 1.2, greater thanor equal to 1.3, greater than or equal to 1.4, greater than or equal to1.5, greater than or equal to 1.6, greater than or equal to 1.7, greaterthan or equal to 1.8, or greater than or equal to 1.9. In otherembodiments, the R₂O:Al₂O₃ ratio is less than or equal to 2.0, less thanor equal to 1.9, less than or equal to 1.8, less than or equal to 1.7,less than or equal to 1.6, less than or equal to 1.5, less than or equalto 1.4, less than or equal to 1.3, less than or equal to 1.2, or lessthan or equal to 1.1. In yet other embodiments, the R₂O:Al₂O₃ ratio isfrom greater than or equal to 0.9 to less than or equal to 1.9, fromgreater than or equal to 1.0 to less than or equal to 1.8, from greaterthan or equal to 1.1 to less than or equal to 1.7, from greater than orequal to 1.2 to less than or equal to 1.6, or from greater than or equalto 1.3 to less than or equal to 1.5. In further embodiments, theR₂O:Al₂O₃ ratio is from greater than or equal to 1.0 to less than orequal to 2.00, such as from greater than or equal to 1.3 to less than orequal to 1.9, or from greater than or equal to 1.3 to less than or equalto 1.5.

In some embodiments, the concentration of CaO to the sum of theconcentration of CaO and the concentration of MgO in mol. % (i.e.,(CaO/(CaO+MgO)) should be minimized. Specifically, it has beendetermined that (CaO/(CaO+MgO)) should be less than or equal to 0.5. Insome embodiments (CaO/(CaO+MgO)) is less than or equal to 0.3 or evenless than or equal to 0.2. In some other embodiments (CaO/(CaO+MgO)) mayeven be less than or equal to 0.1.

The glass composition may, in embodiments, comprise a Li₂O:SiO₂ ratiofrom greater than or equal to 0.01 to less than or equal to 0.17. Insome embodiments, the Li₂O:SiO₂ ratio is greater than or equal to 0.02,greater than or equal to 0.04, greater than or equal to 0.06, greaterthan or equal to 0.08, greater than or equal to 0.10, greater than orequal to 0.12, greater than or equal to 0.14, or greater than or equalto 0.16. In other embodiments, the Li₂O:SiO₂ ratio is less than or equalto 0.02, less than or equal to 0.04, less than or equal to 0.06, lessthan or equal to 0.08, less than or equal to 0.10, less than or equal to0.12, less than or equal to 0.14, or less than or equal to 0.16. In yetother embodiments, the Li₂O:SiO₂ ratio is from greater than or equal to0.02 to less than or equal to 0.16, from greater than or equal to 0.04to less than or equal to 0.14, from greater than or equal to 0.06 toless than or equal to 0.12, or from greater than or equal to 0.08 toless than or equal to 0.1. In further embodiments, the Li₂O:SiO₂ ratiomay be from greater than or equal to 0.06 to less than or equal to 0.12,such as from 0.06 to less than or equal to 0.11, or even from 0.07 toless than or equal to 0.11.

The glass composition may, in embodiments, comprise a Li₂O:(SiO₂+Al₂O₃)ratio from greater than or equal to 0.01 to less than or equal to 0.16.In some embodiments, the Li₂O:SiO₂ ratio is greater than or equal to0.02, greater than or equal to 0.04, greater than or equal to 0.06,greater than or equal to 0.08, greater than or equal to 0.10, greaterthan or equal to 0.12, greater than or equal to 0.14, or greater than orequal to 0.15. In other embodiments, the Li₂O:SiO₂ ratio is less than orequal to 0.02, less than or equal to 0.04, less than or equal to 0.06,less than or equal to 0.08, less than or equal to 0.10, less than orequal to 0.12, less than or equal to 0.14, or less than or equal to0.15. In yet other embodiments, the Li:SiO₂ ratio is from greater thanor equal to 0.02 to less than or equal to 0.15, from greater than orequal to 0.04 to less than or equal to 0.14, from greater than or equalto 0.06 to less than or equal to 0.12, or from greater than or equal to0.08 to less than or equal to 0.1. In further embodiments, the Li₂O:SiO₂ratio may be from greater than or equal to 0.06 to less than or equal to0.12, such as from 0.06 to less than or equal to 0.11, or even from 0.07to less than or equal to 0.11.

Without limiting compositions possibly chosen individually from each ofthe various components recited above, in some embodiments, the glasscomposition may comprise from greater than or equal to 68.00 mol % toless than or equal to 81.00 mol % SiO₂; from greater than or equal to4.00 mol % to less than or equal to 11.00 mol % Al₂O₃; from greater thanor equal to 0.10 mol % to less than or equal to 16.00 mol % Li₂O; fromgreater than or equal to 0.10 mol % to less than or equal to 12.00 mol %Na₂O; from greater than or equal to 0.00 mol % to less than or equal to5.00 mol % K₂O; from greater than or equal to 0.10 mol % to less than orequal to 8.00 mol % MgO; from greater than or equal to 0.10 mol % toless than or equal to 5.00 mol % CaO; from greater than or equal to 0.00mol % to less than or equal to 0.20 mol % fining agent, wherein theglass pharmaceutical package is delamination resistant, and the glasspharmaceutical package has class 1 or class 2 chemical durability inacid, base, and water. In other embodiments, and without limitation, theglass composition may comprise from greater than or equal to 74.00 mol %to less than or equal to 79.00 mol % SiO₂, from greater than or equal to5.00 mol % to less than or equal to 11.00 mol % Al₂O₃, from greater thanor equal to 0.10 mol % to less than or equal to 14.00 mol % Li₂O, fromgreater than or equal to 0.10 mol % to less than or equal to 10.00 mol %Na₂O, from greater than or equal to 0.0 mol % to less than or equal to5.00 mol % K₂O, from greater than or equal to 0.10 mol % to less than orequal to 8.00 mol % MgO, from greater than or equal to 0.10 mol % toless than or equal to 5.00 mol % CaO, and from greater than or equal to0.00 mol % to less than or equal to 0.20 mol % fining agent.

Glass compositions disclosed in embodiments herein may be free fromdelamination. Delamination refers to a phenomenon in which glassparticles are released from the surface of the glass following a seriesof leaching, corrosion, and/or weathering reactions. In general, theparticles are silica-rich flakes of glass which originate from theinterior surface of the container as a result of the leaching ofmodifier ions or weak network formers, such as, for example, sodium,into a solution contained within the container. These flakes maygenerally be from 1 nm to 2 μm thick with a width greater than about 50μm. As these flakes are primarily composed of silica, the flakesgenerally do not further degrade after being released from the surfaceof the glass.

It is believed that delamination of the silica-rich glass flakes fromthe interior surfaces of the glass containers is due to thecompositional characteristics of the glass container in its as receivedcondition. Specifically, the high silica content of alkalialuminosilicate glasses causes the glass to have relatively high meltingand forming temperatures. However, other components in the glass, suchas, for example, boron, melt and/or vaporize at much lower temperatures.In particular, the boron species in conventional glasses are volatileand evaporate from the surface of the glass at the high temperaturesnecessary to form and reform the glass.

Specifically, glass stock, such as a glass tube or the like, is reformedinto glass containers, such as, for example, glass vials or the like, athigh temperatures and in direct flames. The high temperatures needed athigher equipment speeds cause the more volatile boron species toevaporate from regions of the surface of the glass. When thisevaporation occurs within the interior volume of the glass container,the volatilized boron species are re-deposited in other areas of theglass container surface causing compositional heterogeneities in theglass container surface, particularly with respect to the near-surfaceregions of the interior of the glass container (i.e., those regions ator directly adjacent to the interior surfaces of the glass container).However, the glass compositions disclosed and described herein areformulated so that boron is not included in the glass composition, thusreducing the amount of delamination that occurs in the glass article.The delamination may be measured by the delamination factor disclosed inU.S. Pat. No. 9,428,302, which is incorporated herein by reference inits entirety. In some embodiments, the glass may have a delaminationfactor less than or equal to 10, such as less than or equal to 8, oreven less than or equal to 6.

Physical properties of Li containing aluminosilicate glass compositionsas disclosed above will now be discussed. The properties discussed belowshow the results of adding lithium to aluminosilicate glasses or alkalialuminosilicate glasses. These physical properties can be achieved bymodifying the component amounts of the Li containing aluminosilicateglass composition, as will be discussed in more detail with reference tothe examples. Heretofore, the effect that lithium has on the physicalproperties of glass compositions was not clearly understood.

Glass compositions according to embodiments may have a density fromgreater than or equal to 2.25 g/cm³ to less than or equal to 2.50 g/cm³,such as from greater than or equal to 2.30 g/cm³ to less than or equalto 2.45 g/cm³, from greater than or equal to 2.35 g/cm³ to less than orequal to 2.45 g/cm³, or from greater than or equal to 2.40 g/cm³ to lessthan or equal to 2.45 g/cm³. In other embodiments, the glass compositionmay have a density from greater than or equal to 2.25 g/cm³ to less thanor equal to 2.40 g/cm³, from greater than or equal to 2.25 g/cm³ to lessthan or equal to 2.35 g/cm³, or from greater than or equal to 2.25 g/cm³to less than or equal to 2.30 g/cm³. In some embodiments, the glasscompositions may have a density of about 2.35 g/cm³, about 2.36 g/cm³,about 2.37 g/cm³, about 2.38 g/cm³, or about 2.39 g/cm³. Generally, aslarger, more dense alkali metal cations, such as Na⁺ or K⁺, are replacedwith smaller alkali metal cations, such as Li⁺, in an alkalialuminosilicate glass composition, the density of the glass compositiondecreases. Accordingly, the higher the amount of lithium in the glasscomposition, the less dense the glass composition will be.

Similarly to glass density discussed above, glass compositions accordingto embodiments may have a molar volume from greater than or equal to24.00 cm³/mol to less than or equal to 27.00 cm³/mol, such as fromgreater than or equal to 24.50 cm³/mol to less than or equal to 27.00cm³/mol, from greater than or equal to 25.00 cm³/mol to less than orequal to 27.00 cm³/mol, from greater than or equal to 25.50 cm³/mol toless than or equal to 27.00 cm³/mol, from greater than or equal to 26.00cm³/mol to less than or equal to 27.00 cm³/mol, or from greater than orequal to 26.50 cm³/mol to less than or equal to 27.00 cm³/mol. In otherembodiments, the glass composition may have a molar volume from greaterthan or equal to 24.00 cm³/mol to less than or equal to 26.50 cm³/mol,from greater than or equal to 24.00 cm³/mol to less than or equal to26.00 cm³/mol, from greater than or equal to 24.00 cm³/mol to less thanor equal to 25.50 cm³/mol, from greater than or equal to 24.00 cm³/molto less than or equal to 25.00 cm³/mol, or from greater than or equal to24.00 cm³/mol to less than or equal to 24.50 cm³/mol. In yet otherembodiments, the glass composition may have a molar volume of about24.80 cm³/mol, 25.00 cm³/mol, about 25.20 cm³/mol, about 25.40 cm³/mol,about 25.60 cm³/mol, about 25.80 cm³/mol, or about 26.00 cm³/mol. Thedensity of the glass was measured by a buoyancy method for homogenous,nonporous, water-insoluble materials at or near 25° C., as described inASTM C693. As was the case with density, generally as larger alkalimetal ions, such as Na⁺ and K⁺, are replaced with smaller alkali ions,such as Li^(t), in an alkali aluminosilicate glass composition, themolar volume of the glass composition decreases. The molar volume wascalculated from glass density (ρ) and average molar weight (M) of theglass composition by the following equation: V_(M)=M/ρ.

The strain point, annealing point, and softening point of glasscompositions may also be affected by the amount of lithium in the glasscomposition. As the amount of lithium in the glass compositionincreases, the amount of other, larger alkali metal cations, such as Na⁺and K⁺, decreases. It has been found that a minimum strain point, aminimum annealing point, and a minimum softening point occurs wherelithium has replaced sodium such that the sodium content is about 4 mol%. In embodiments, the strain point of glass compositions may be fromgreater than or equal to 450° C. to less than or equal to 625° C., suchas from greater than or equal to 475° C. to less than or equal to 600°C., from greater than or equal to 500° C. to less than or equal to 575°C., from greater than or equal to 515° C. to less than or equal to 560°C., or from greater than or equal to 530° C. to less than or equal to550° C. In other embodiments, the strain point of the glass compositionmay be from greater than or equal to 500° C. to less than or equal to560° C., such as from greater than or equal to 510° C. to less than orequal to 560° C., from greater than or equal to 520° C. to less than orequal to 560° C., from greater than or equal to 530° C. to less than orequal to 560° C., or from greater than or equal to 540° C. to less thanor equal to 560° C. In yet other embodiments, the strain point of theglass composition may be from greater than or equal to 500° C. to lessthan or equal to 555° C., from greater than or equal to 500° C. to lessthan or equal to 550° C., from greater than or equal to 500° C. to lessthan or equal to 540° C., from greater than or equal to 500° C. to lessthan or equal to 530° C., or from greater than or equal to 500° C. toless than or equal to 520° C. The beam bending viscosity method measuresthe viscosity of inorganic glass from 10¹² to 10¹⁴ poise versustemperature and from this measurement estimates the strain point of theglass. This method conforms to ASTM C598

In embodiments, the annealing point of glass compositions may be fromgreater than or equal to 500° C. to less than or equal to 675° C., suchas from greater than or equal to 525° C. to less than or equal to 650°C., from greater than or equal to 550° C. to less than or equal to 625°C., from greater than or equal to 565° C. to less than or equal to 615°C., or from greater than or equal to 580° C. to less than or equal to600° C. In other embodiments, the annealing point of the glasscomposition may be from greater than or equal to 550° C. to less than orequal to 625° C., such as from greater than or equal to 560° C. to lessthan or equal to 625° C., from greater than or equal to 570° C. to lessthan or equal to 625° C., from greater than or equal to 580° C. to lessthan or equal to 625° C., or from greater than or equal to 590° C. toless than or equal to 625° C. In yet other embodiments, the annealingpoint of the glass composition may be from greater than or equal to 550°C. to less than or equal to 615° C., from greater than or equal to 550°C. to less than or equal to 610° C., from greater than or equal to 550°C. to less than or equal to 600° C., from greater than or equal to 550°C. to less than or equal to 590° C., or from greater than or equal to550° C. to less than or equal to 580° C. The beam bending viscositymethod measures the viscosity of inorganic glass from 10¹² to 10¹⁴ poiseversus temperature and from this measurement estimates the annealingpoint of the glass. This method conforms to ASTM C598

In embodiments, the softening point of glass compositions may be fromgreater than or equal to 750° C. to less than or equal to 950° C., suchas from greater than or equal to 775° C. to less than or equal to 925°C., from greater than or equal to 750° C. to less than or equal to 900°C., from greater than or equal to 800° C. to less than or equal to 875°C., or from greater than or equal to 825° C. to less than or equal to850° C. In other embodiments, the softening point of the glasscomposition may be from greater than or equal to 800° C. to less than orequal to 925° C., such as from greater than or equal to 815° C. to lessthan or equal to 925° C., from greater than or equal to 830° C. to lessthan or equal to 925° C., from greater than or equal to 845° C. to lessthan or equal to 925° C., or from greater than or equal to 860° C. toless than or equal to 925° C. In yet other embodiments, the softeningpoint of the glass composition may be from greater than or equal to 800°C. to less than or equal to 915° C., from greater than or equal to 800°C. to less than or equal to 900° C., from greater than or equal to 800°C. to less than or equal to 885° C., from greater than or equal to 800°C. to less than or equal to 870° C., or from greater than or equal to800° C. to less than or equal to 850° C. The parallel place viscositymethod measures viscosity from 10⁷ to 10⁹ poise versus temperature forinorganic glass and from this estimates a “normal softening point.” Thismethod is similar to ASTM C1351M.

Additionally, the amount of lithium in the glass composition alsoaffects the CTE of the glass composition. As lithium replaces largeralkali cations, such as Na⁺ and K⁺, in the alkali aluminosilicate glasscomposition, the CTE of the glass composition decreases. In embodiments,the CTE of the glass composition may be from greater than or equal to4.20 ppm/° C. to less than or equal to 7.00 ppm/° C., such as fromgreater than or equal to 4.50 ppm/° C. to less than or equal to 6.90ppm/° C., from greater than or equal to 4.70 ppm/° C. to less than orequal to 6.80 ppm/° C., from greater than or equal to 4.90 ppm/° C. toless than or equal to 6.70 ppm/° C., from greater than or equal to 5.00ppm/° C. to less than or equal to 6.80 ppm/° C., from greater than orequal to 5.20 ppm/° C. to less than or equal to 6.70 ppm/° C., fromgreater than or equal to 5.40 ppm/° C. to less than or equal to 6.60ppm/° C., from greater than or equal to 5.60 ppm/° C. to less than orequal to 6.50 ppm/° C., from greater than or equal to 5.80 ppm/° C. toless than or equal to 6.40 ppm/° C., or from greater than or equal to6.00 ppm/° C. to less than or equal to 6.30 ppm/° C. In otherembodiments, the glass composition may have a CTE from greater than orequal to 5.00 ppm/° C. to less than or equal to 7.00 ppm/° C., fromgreater than or equal to 5.20 ppm/° C. to less than or equal to 7.00ppm/° C., from greater than or equal to 5.40 ppm/° C. to less than orequal to 7.00 ppm/° C., from greater than or equal to 5.60 ppm/° C. toless than or equal to 7.00 ppm/° C., from greater than or equal to 5.80ppm/° C. to less than or equal to 7.00 ppm/° C., from greater than orequal to 6.00 ppm/° C. to less than or equal to 7.00 ppm/° C., fromgreater than or equal to 6.20 ppm/° C. to less than or equal to 7.00ppm/° C., from greater than or equal to 6.40 ppm/° C. to less than orequal to 7.00 ppm/° C., from greater than or equal to 6.60 ppm/° C. toless than or equal to 7.00 ppm/° C., from greater than or equal to 6.80ppm/° C. to less than or equal to 7.00 ppm/° C. In yet otherembodiments, the glass composition has a CTE from the glass compositionmay have a CTE from greater than or equal to 5.00 ppm/° C. to less thanor equal to 6.80 ppm/° C., the glass composition may have a CTE fromgreater than or equal to 5.00 ppm/° C. to less than or equal to 6.60ppm/° C., the glass composition may have a CTE from greater than orequal to 5.00 ppm/° C. to less than or equal to 6.40 ppm/° C., the glasscomposition may have a CTE from greater than or equal to 5.00 ppm/° C.to less than or equal to 6.20 ppm/° C., the glass composition may have aCTE from greater than or equal to 5.00 ppm/° C. to less than or equal to6.00 ppm/° C., the glass composition may have a CTE from greater than orequal to 5.00 ppm/° C. to less than or equal to 5.80 ppm/° C., the glasscomposition may have a CTE from greater than or equal to 5.00 ppm/° C.to less than or equal to 5.60 ppm/° C., the glass composition may have aCTE from greater than or equal to 5.00 ppm/° C. to less than or equal to5.40 ppm/° C., the glass composition may have a CTE from greater than orequal to 5.00 ppm/° C. to less than or equal to 5.20 ppm/° C. Adilatometer method was used to determine a mean coefficient of linearthermal expansion (CTE) of a solid material, such as, for example,glass. This method conforms to ASTM E228.

The amount of lithium in a glass composition also has an effect on theliquidus temperature of the glass composition. Namely, as lithiumreplaces larger alkali cations, such as Na⁺ and K⁺, in an alkalialuminosilicate glass composition, the liquidus temperature of the glasscomposition increases. In embodiments, the liquidus temperature is fromgreater than or equal to 950° C. to less than or equal to 1250° C., suchas from greater than or equal to 970° C. to less than or equal to 1230°C., from greater than or equal to 1000° C. to less than or equal to1210° C., from greater than or equal to 1020° C. to less than or equalto 1190° C., from greater than or equal to 1040° C. to less than orequal to 1170° C., from greater than or equal to 1060° C. to less thanor equal to 1150° C., from greater than or equal to 1080° C. to lessthan or equal to 1130° C., or from greater than or equal to 1090° C. toless than or equal to 1110° C. In other embodiments, the glasscomposition has a liquidus temperature from greater than or equal to1000° C. to less than or equal to 1230° C., from greater than or equalto 1020° C. to less than or equal to 1230° C., from greater than orequal to 1040° C. to less than or equal to 1230° C., from greater thanor equal to 1060° C. to less than or equal to 1230° C., from greaterthan or equal to 1080° C. to less than or equal to 1230° C., fromgreater than or equal to 1100° C. to less than or equal to 1230° C.,from greater than or equal to 1120° C. to less than or equal to 1230°C., from greater than or equal to 1140° C. to less than or equal to1230° C., from greater than or equal to 1160° C. to less than or equalto 1230° C., from greater than or equal to 1180° C. to less than orequal to 1230° C., from greater than or equal to 1200° C. to less thanor equal to 1230° C. In yet other embodiments, the glass composition hasa liquidus temperature from greater than or equal to 1000° C. to lessthan or equal to 1210° C., from greater than or equal to 1000° C. toless than or equal to 1190° C., from greater than or equal to 1000° C.to less than or equal to 1170° C., from greater than or equal to 1000°C. to less than or equal to 1150° C., from greater than or equal to1000° C. to less than or equal to 1130° C., from greater than or equalto 1110° C. to less than or equal to 1230° C., from greater than orequal to 1000° C. to less than or equal to 1090° C., from greater thanor equal to 1000° C. to less than or equal to 1070° C., from greaterthan or equal to 1000° C. to less than or equal to 1050° C., or fromgreater than or equal to 1000° C. to less than or equal to 1030° C. Theliquidus temperature was measured by the gradient furnace method. Thismethod conforms to ASTM C829-81 Standard Practices for Measurement ofLiquidus Temperature of Glass.

The amount of lithium in a glass composition also has an effect on theliquidus viscosity of the glass composition. Namely, as lithium replaceslarger alkali cations, such as Na⁺ and K⁺, in an alkali aluminosilicateglass composition, the liquidus viscosity of the glass compositionincreases. In embodiments, the Log of liquidus viscosity is from greaterthan or equal to 3.50 poise to less than or equal to 6.00 poise, such asfrom greater than or equal to 3.75 poise to less than or equal to 6.00poise, greater than or equal to 4.00 poise to less than or equal to 6.00poise, greater than or equal to 4.25 poise to less than or equal to 6.00poise, from greater than or equal to 4.50 poise to less than or equal to6.00 poise, greater than or equal to 4.75 poise to less than or equal to6.00 poise, greater than or equal to 5.00 poise to less than or equal to6.00 poise, greater than or equal to 5.25 poise to less than or equal to6.00 poise, greater than or equal to 5.50 poise to less than or equal to6.00 poise, or greater than or equal to 5.75 poise to less than or equalto 6.00 poise. In other embodiments, the Log of liquidus viscosity isfrom greater than or equal to 3.50 poise to less than or equal to 5.75poise, such as from greater than or equal to 3.50 poise to less than orequal to 5.50 poise, greater than or equal to 3.50 poise to less than orequal to 5.25 poise, greater than or equal to 3.50 poise to less than orequal to 5.00 poise, from greater than or equal to 3.50 poise to lessthan or equal to 4.75 poise, greater than or equal to 3.50 poise to lessthan or equal to 4.50 poise, greater than or equal to 3.50 poise to lessthan or equal to 4.25 poise, greater than or equal to 3.50 poise to lessthan or equal to 4.00 poise, or greater than or equal to 3.50 poise toless than or equal to 3.75 poise. The liquidus viscosity was measured bythe gradient furnace method. This method conforms to ASTM C829-81Standard Practices for Measurement of Liquidus Temperature of Glass.

The addition of lithium to the glass composition also affects theYoung's modulus, shear modulus, and Poisson's ratio of the glasscomposition. Namely, as lithium replaces larger alkali cations, such asNa⁺ and K⁺, in an alkali aluminosilicate glass composition, the Young'smodulus, shear modulus, and Poisson's ratio of the glass compositionincreases. In embodiments, the Young's modulus of a glass compositionmay be from greater than or equal to 10.00 mpsi to less than or equal to12.00 mpsi, such as from greater than or equal to 10.20 mpsi to lessthan or equal to 11.80 mpsi, from greater than or equal to 10.40 mpsi toless than or equal to 11.60 mpsi, from greater than or equal to 10.60mpsi to less than or equal to 11.40 mpsi, or from greater than or equalto 10.80 mpsi to less than or equal to 11.20 mpsi. In other embodiments,the Young's modulus of the glass composition may be from greater than orequal to 10.20 mpsi to less than or equal to 12.00 mpsi, from greaterthan or equal to 10.40 mpsi to less than or equal to 12.00 mpsi, fromgreater than or equal to 10.60 mpsi to less than or equal to 12.00 mpsi,from greater than or equal to 10.80 mpsi to less than or equal to 12.00mpsi, from greater than or equal to 11.00 mpsi to less than or equal to12.00 mpsi, from greater than or equal to 11.20 mpsi to less than orequal to 12.00 mpsi, from greater than or equal to 11.40 mpsi to lessthan or equal to 12.00 mpsi, from greater than or equal to 11.60 mpsi toless than or equal to 12.00 mpsi, or from greater than or equal to 11.80mpsi to less than or equal to 12.00 mpsi. In yet other embodiments, theYoung's modulus may be from greater than or equal to 10.00 mpsi to lessthan or equal to 11.80 mpsi, from greater than or equal to 10.00 mpsi toless than or equal to 11.60 mpsi, from greater than or equal to 10.00mpsi to less than or equal to 11.40 mpsi, from greater than or equal to10.00 mpsi to less than or equal to 11.20 mpsi, from greater than orequal to 10.00 mpsi to less than or equal to 11.00 mpsi, from greaterthan or equal to 10.00 mpsi to less than or equal to 10.80 mpsi, fromgreater than or equal to 10.00 mpsi to less than or equal to 10.60 mpsi,from greater than or equal to 10.00 mpsi to less than or equal to 10.40mpsi, or from greater than or equal to 10.00 mpsi to less than or equalto 10.20 mpsi. Young's modulus was measured by Resonant UltrasoundSpectroscopy, which conforms to ASTM C623.

According to some embodiments, the glass composition may have a shearmodulus of from greater than or equal to 4.00 mpsi to less than or equalto 5.00 mpsi, such as from greater than or equal to 4.10 mpsi to lessthan or equal to 4.90 mpsi, from greater than or equal to 4.20 mpsi toless than or equal to 4.80 mpsi, from greater than or equal to 4.30 mpsito less than or equal to 4.70 mpsi, or from greater than or equal to4.40 mpsi to less than or equal to 4.50 mpsi. In other embodiments theglass composition may have a shear modulus from greater than or equal to4.10 mpsi to less than or equal to 5.00 mpsi, from greater than or equalto 4.20 mpsi to less than or equal to 5.00 mpsi, from greater than orequal to 4.30 mpsi to less than or equal to 5.00 mpsi, from greater thanor equal to 4.40 mpsi to less than or equal to 5.00 mpsi, from greaterthan or equal to 4.50 mpsi to less than or equal to 5.00 mpsi, fromgreater than or equal to 4.60 mpsi to less than or equal to 5.00 mpsi,from greater than or equal to 4.70 mpsi to less than or equal to 5.00mpsi, from greater than or equal to 4.80 mpsi to less than or equal to5.00 mpsi, or from greater than or equal to 4.90 mpsi to less than orequal to 5.00 mpsi. In yet other embodiments, the glass composition mayhave a shear modulus from greater than or equal to 4.00 mpsi to lessthan or equal to 4.90 mpsi, from greater than or equal to 4.00 mpsi toless than or equal to 4.80 mpsi, from greater than or equal to 4.00 mpsito less than or equal to 4.70 mpsi, from greater than or equal to 4.00mpsi to less than or equal to 4.60 mpsi, from greater than or equal to4.00 mpsi to less than or equal to 4.50 mpsi, from greater than or equalto 4.00 mpsi to less than or equal to 4.40 mpsi, from greater than orequal to 4.00 mpsi to less than or equal to 4.30 mpsi, from greater thanor equal to 4.00 mpsi to less than or equal to 4.20 mpsi, or fromgreater than or equal to 4.00 mpsi to less than or equal to 4.10 mpsi.The shear modulus was measured by Resonant Ultrasound Spectroscopy,which conforms to ASTM C623.

In addition to the physical properties discussed above, adding lithiumto the glass composition may increase the chemical durability of theglass composition in acids, bases, and water (hydrolytic durability).The durability of the glass composition in acid is measured according toDIN 12116, the durability of the glass composition in a base is measuredaccording to ISO 695, and the hydrolytic durability of the glasscomposition is measure by ISO 720. In embodiments, the glasscompositions have class 1 or class 2 durability in acid, base, andwater. In other embodiments, the glass composition may have class 1durability in acid, base, and water.

The durability of the glass composition in acid, according toembodiments, is from greater than or equal to 0.0 mg/dm² to less than orequal to 1.5 mg/dm², such as from greater than or equal to 0.0 mg/dm² toless than or equal to 1.2 mg/dm², from greater than or equal to 0.0mg/dm² to less than or equal to 1.0 mg/dm², from greater than or equalto 0.0 mg/dm² to less than or equal to 0.8 mg/dm², from greater than orequal to 0.0 mg/dm² to less than or equal to 0.6 mg/dm², or from greaterthan or equal to 0.0 mg/dm² to less than or equal to 0.4 mg/dm². Inother embodiments, the durability of the glass composition to acid maybe from greater than or equal to 0.0 mg/dm² to less than or equal to 0.7mg/dm², from greater than or equal to 0.0 mg/dm² to less than or equalto 0.6 mg/dm², from greater than or equal to 0.0 mg/dm² to less than orequal to 0.5 mg/dm², from greater than or equal to 0.0 mg/dm² to lessthan or equal to 0.4 mg/dm², from greater than or equal to 0.0 mg/dm² toless than or equal to 0.3 mg/dm², from greater than or equal to 0.0mg/dm² to less than or equal to 0.2 mg/dm², or from greater than orequal to 0.0 mg/dm² to less than or equal to 0.1 mg/dm². In yet otherembodiments, the durability of the glass composition to acid is fromgreater than or equal to 0.3 mg/dm² to less than or equal to 1.5 mg/dm²,from greater than or equal to 0.4 mg/dm² to less than or equal to 1.2mg/dm², from greater than or equal to 0.5 mg/dm² to less than or equalto 1.0 mg/dm², from greater than or equal to 0.6 mg/dm² to less than orequal to 0.9 mg/dm², or from greater than or equal to 0.7 mg/dm² to lessthan or equal to 0.8 mg/dm².

The durability of the glass composition in a base, according toembodiments, may be from greater than or equal to 0 mg/dm² to less thanor equal to 175 mg/dm², such as from greater than or equal to 0 mg/dm²to less than or equal to 150 mg/dm², from greater than or equal to 0mg/dm² to less than or equal to 125 mg/dm², or from greater than orequal to 0 mg/dm² to less than or equal to 100 mg/dm². In otherembodiments, the durability of the glass composition a base is fromgreater than or equal to 0 mg/dm² to less than or equal to 75 mg/dm²,from greater than or equal to 0 mg/dm² to less than or equal to 65mg/dm², from greater than or equal to 0 mg/dm² to less than or equal to55 mg/dm², from greater than or equal to 0 mg/dm² to less than or equalto 45 mg/dm², from greater than or equal to 0 mg/dm² to less than orequal to 35 mg/dm², from greater than or equal to 0 mg/dm² to less thanor equal to 25 mg/dm², or from greater than or equal to 0 mg/dm² to lessthan or equal to 15 mg/dm².

The hydrolytic durability of the glass composition, according toembodiments, may be from greater than or equal to 0 μg/g to less than orequal to 100 μg/g, such as from greater than or equal to 0 μg/g to lessthan or equal to 90 μg/g, from greater than or equal to 0 μg/g to lessthan or equal to 80 μg/g, from greater than or equal to 0 μg/g to lessthan or equal to 70 μg/g, or from greater than or equal to 0 μg/g toless than or equal to 75 μg/g. In other embodiments, the hydrolyticdurability of the glass composition may from greater than or equal to 0μg/g to less than or equal to 62 μg/g, from greater than or equal to 0μg/g to less than or equal to 60 μg/g, from greater than or equal to 0μg/g to less than or equal to 55 μg/g, from greater than or equal to 0μg/g to less than or equal to 50 μg/g, from greater than or equal to 0μg/g to less than or equal to 45 μg/g, from greater than or equal to 0μg/g to less than or equal to 40 μg/g, from greater than or equal to 0μg/g to less than or equal to 35 μg/g, from greater than or equal to 0μg/g to less than or equal to 30 μg/g, or from greater than or equal to0 μg/g to less than or equal to 25 μg/g. In yet other embodiments, thehydrolytic durability of the glass composition may be from greater thanor equal to 10 μg/g to less than or equal to 100 μg/g, from greater thanor equal to 20 μg/g to less than or equal to 90 μg/g, from greater thanor equal to 30 μg/g to less than or equal to 80 μg/g, from greater thanor equal to 40 μg/g to less than or equal to 70 μg/g, or from greaterthan or equal to 50 μg/g to less than or equal to 60 μg/g.

The distribution of alkali metals in the glass composition also has aneffect on the durability of the glass. For instance, if the total amountof alkali metals in the glass composition is kept constant, the amountof Na₂O to the total alkali metals, the amount of potassium to the totalalkali metals, and the amount of lithium to the total alkali metals willaffect the durability of the glass. In embodiments, the best hydrolyticdurability and durability in a base, in accordance with ISO 720 and ISO695, respectively, is achieved when the amount of Li₂O relative to thetotal alkali metal oxides content is from greater than or equal to 60%to less than or equal to 70%, the amount of Na₂O to the total alkalimetal oxides content is from greater than or equal to 12% to less thanor equal to 22%, and the amount of potassium relative to the totalalkali metal oxides content is from greater than or equal to 12% to lessthan or equal to 22%. In other embodiments, the amount of Li₂O relativeto the total alkali metal oxides content is from greater than or equalto 62% to less than or equal to 68%, the amount of Na₂O to the totalalkali metal oxides content is from greater than or equal to 14% to lessthan or equal to 20%, and the amount of potassium relative to the totalalkali metal oxides content is from greater than or equal to 14% to lessthan or equal to 20%. In still other embodiments, the amount of Li₂Orelative to the total alkali metal oxides content is from greater thanor equal to 64% to less than or equal to 66%, the amount of Na₂O to thetotal alkali metal oxides content is from greater than or equal to 15%to less than or equal to 18%, and the amount of potassium relative tothe total alkali metal oxides content is from greater than or equal to15% to less than or equal to 18%. It should be understood that glasseshaving an alkali distribution outside of the above ranges may still havesufficient hydrolytic and basic durability.

As mentioned above, in embodiments, the Li containing aluminosilicateglass compositions can be strengthened, such as by ion exchange, makinga glass that is damage resistant for applications such as, but notlimited to, glass packaging for pharmaceuticals. It was found thatadding lithium provides many advantages, as disclosed herein. Inparticular, the glass compositions of conventional glass packaging havehigh amounts of sodium and do not include high amounts of lithium. Theseconventional glasses do not have good compressive stress profiles, andthe compressive stress, central tension, and depth of compression islimited in conventional glass compositions. By comparison, compressivestress profiles of boroaluminosilicate glasses are more ideal than thecompressive stress profiles of conventional glasses for pharmaceuticalpackaging. However, as discusses above, including boron in the glasscomposition can lead to increased delamination, which is not acceptablein pharmaceutical packaging. Thus, glasses of embodiments disclosedherein are designed to have compressive stress profiles similar to thoseof boroaluminosilicate glasses without the use of boron.

To improve the compressive stress profile of the glass composition,sodium is replaced with lithium. By adding lithium to the glasscomposition, more control can be exercised over the ion exchange processbecause, for example, both lithium and sodium ions in the glass can beexchanged with either sodium or potassium ions, respectively, in the ionexchange solution. This allows a quicker ion exchange process thatallows one to ion exchange through a decreasing slope of the ionexchange profile to the point of central tension. This allows one totune the CT, DOC, DOL_(k), and CS to values suitable for a particularpurpose. For instance, as disclosed in more detail below, the CS, DOC,and CT can be tuned so that a glass fractures into multiple pieces uponimpact, which allows one to more easily recognize the fracture, or aglass can be made to resist multiple fractures.

In view of the above, lithium is added to glass compositions to improvethe compressive stress profiles of the glass. However, it wassurprisingly found that the addition of lithium to the glass compositionalso improved the hydrolytic durability of the glass as well asdecreasing the annealing temperature and softening point, as referred toabove. Lithium increases the liquidus temperature and decreases liquidusviscosity of the glass. Therefore, the amount of lithium must bebalanced so that the glass is still formable while providing thebenefits discussed above. The effect that lithium has on the ionexchange ability of the glass is discusses below.

With reference to FIG. 1 , the glass has a first region 120 and secondregion 122 under compressive stress. The compressive stress of the firstregion 120 extends from a surface 110 to a depth of the glass d₁. Thecompressive stress of the second region 122 extends from a surface 112to a depth of the glass d₂. Between the first region 120 and the secondregion 122 is a third region 130 that is under tension and, therefore,comprises an internal tensile stress. The third region 130 extends fromone of the first region 120 and the second region 122 to the other ofthe first region 120 or the second region 122. The depth of compression(DOC) as used herein refers to a depth from the surface of the glassarticle (e.g., 110) to the region of the glass article that is undertension (e.g., 130). In other words the DOC of a glass is measured fromthe surface of a glass to the point where the stress changes fromcompressive stress to tensile stress. Herein, the DOC is referred to asa portion of the entire thickness (t) of the glass. For instance, if theDOC is 25% of the glass thickness, it will be referred to herein as 0.25t.

The compressive stress (CS) has a maximum at the surface of the glass,and the CS varies with distance d from the surface according to afunction, such as the stress function shown in FIG. 2 . Referring againto FIG. 1 , a first region 120 extends from first surface 110 to a depthd₁ and a second region 122 extends from a second surface 112 to a depthd₂. Together, these segments define a surface compression or surface CSof glass 100. In some embodiments, the surface CS is at least 350 MPa,such as at least 375 MPa, at least 400 MPa, at least 425 MPa, at least450 MPa, or at least 475 MPa. In other embodiments, the surface CS isless than or equal to 525 MPa, such as less than or equal to 500 MPa. Inyet other embodiments, the surface CS may be from greater than or equalto 350 MPa to less than or equal to 500 MPa, such as from greater thanor equal to 375 MPa to less than or equal to 500 MPa, from greater thanor equal to 400 MPa to less than or equal to 500 MPa, from greater thanor equal to 425 MPa to less than or equal to 500 MPa, from greater thanor equal to 450 MPa to less than or equal to 500 MPa, or from greaterthan or equal to 475 MPa to less than or equal to 500 MPa.

The depth of layer DOL_(k), as used herein refers to the depth thatpotassium diffuses into the glass from the ion exchange process. TheDOL_(k) of each of first and second regions 120, 122 is from greaterthan or equal to 2 μm to less than or equal to 45 such as from greaterthan or equal to 5 μm to less than or equal to 40 from greater than orequal to 10 μm to less than or equal to 35 from greater than or equal to15 μm to less than or equal to or from greater than or equal to 20 μm toless than or equal to 25 In other embodiments, the DOL_(k) of each ofthe first and second regions 120, 122 is from greater than or equal to10 μm to less than or equal to 40 μm, from greater than or equal to 15μm to less than or equal to 40 μm, from greater than or equal to 20 μmto less than or equal to 40 μm, from greater than or equal to 25 μm toless than or equal to 40 μm, from greater than or equal to 30 μm to lessthan or equal to 40 μm, or from greater than or equal to 35 μm to lessthan or equal to 40 μm. In yet other embodiments, the DOL_(k) of each ofthe first and second regions 120, 122 is from greater than or equal to 2μm to less than or equal to 40 μm, from greater than or equal to 2 μm toless than or equal to 35 μm, from greater than or equal to 2 μm to lessthan or equal to 30 μm, from greater than or equal to 2 μm to less thanor equal to 25 μm, from greater than or equal to 2 μm to less than orequal to 20 μm, from greater than or equal to 2 μm to less than or equalto 15 μm, from greater than or equal to 2 μm to less than or equal to 10μm, or from greater than or equal to 2 μm to less than or equal to 5 μm.

It has also been determined that amount of lithium has an effect on thediffusivity of potassium ions into the glass, which can have an effecton the DOL_(k) of the glass. Generally, as the amount of lithium in theglass increases, the diffusivity of potassium into the glass willdecrease. Without being bound to any particular theory, generallypotassium ions in the ion exchange solution will exchange with sodium inthe glass matrix. Thus, as sodium in the glass matrix is replaced withlithium, there is less sodium in the glass matrix to be replaced withpotassium ions from the ion exchange solution, thereby decreasing thediffusivity of potassium ions. In embodiments, the diffusivity ofpotassium into the glass at 420° C. is from greater than or equal to0.50 μm²/hr to less than or equal to 15.00 μm²/hr, such as from greaterthan or equal to 0.60 μm²/hr to less than or equal to 14.50 μm²/hr,greater than or equal to 0.70 μm²/hr to less than or equal to 14.00μm²/hr, greater than or equal to 1.00 μm²/hr to less than or equal to13.50 μm²/hr, greater than or equal to 1.25 μm²/hr to less than or equalto 13.00 μm²/hr, from greater than or equal to 1.50 μm²/hr to less thanor equal to 12.50 μm²/hr, greater than or equal to 2.00 μm²/hr to lessthan or equal to 11.50 μm²/hr, greater than or equal to 2.25 μm²/hr toless than or equal to 11.00 μm²/hr, greater than or equal to 2.50 μm²/hrto less than or equal to 10.50 μm²/hr, greater than or equal to 2.75μm²/hr to less than or equal to 10.00 μm²/hr, greater than or equal to3.00 μm²/hr to less than or equal to 9.50 μm²/hr, greater than or equalto 3.25 μm²/hr to less than or equal to 9.00 μm²/hr, greater than orequal to 3.50 μm²/hr to less than or equal to 8.50 μm²/hr, greater thanor equal to 3.75 μm²/hr to less than or equal to 8.00 μm²/hr, greaterthan or equal to 4.00 μm²/hr to less than or equal to 7.50 μm²/hr,greater than or equal to 4.25 μm²/hr to less than or equal to 7.00μm²/hr, greater than or equal to 4.50 μm²/hr to less than or equal to6.50 1.1,m²/hr, or greater than or equal to 4.75 μm²/hr to less than orequal to 6.00 μm²/hr. In other embodiments, the diffusivity of potassiuminto the glass at 420° C. is from greater than or equal to 6.00 μm²/hrto less than or equal to 8.00 μm²/hr, greater than or equal to 6.25μm²/hr to less than or equal to 7.75 μm²/hr, from greater than or equalto 6.50 μm²/hr to less than or equal to 7.50 μm²/hr, or greater than orequal to 6.75 μm²/hr to less than or equal to 7.25 μm²/hr.

As mentioned above, in embodiments, the Li containing glass compositionscan be strengthened, such as by ion exchange, making a glass that isdamage resistant. With reference to FIG. 1 , the glass has a first andsecond regions under compressive stress (e.g., layers 120, 122 in FIG. 1) extending from the surface to a depth of compression (DOC) of theglass and a third region (e.g., 130 in FIG. 1 ) under a tensile stressextending from the DOC into the central or interior region of the glass.Central tension (CT) is the maximum tensile stress, which is generallylocated at the center of the third region 130. As used herein, DOCrefers to the depth at which the stress within the glass article changesfrom compressive to tensile. At the DOC, the stress crosses from anegative (compressive) stress to a positive (tensile) stress and thusexhibits a stress value of zero. The CT and DOC values are measuredusing a scattered light polariscope (SCALP) technique known in the art.

According to the convention normally used in the art, compression orcompressive stress is expressed as a negative (<0) stress and tension ortensile stress is expressed as a positive (>0) stress. Throughout thisdescription, however, CS is expressed as a positive or absolutevalue—i.e., as recited herein, CS=|CS|. The compressive stress (CS) hasa maximum at the surface of the glass, and the CS varies with distance dfrom the surface according to a function. Referring again to FIG. 1 , afirst region 120 extends from first surface 110 to a depth d₁ and asecond segment 122 extends from a second surface 112 to a depth d₂.Together, these segments define a compression or CS of glass 100.Compressive stress (including surface CS) is measured by surface stressmeter (FSM) using commercially available instruments such as theFSM-6000, manufactured by Orihara Industrial Co., Ltd. (Japan). Surfacestress measurements rely upon the accurate measurement of the stressoptical coefficient (SOC), which is related to the birefringence of theglass. SOC in turn is measured according to Procedure C (Glass DiscMethod) described in ASTM standard C770-16.

In embodiments, the glass composition may have a CT from greater than orequal to 5 MPa to less than or equal to 160 MPa, such as from greaterthan or equal to 10 MPa to less than or equal to 150 MPa, from greaterthan or equal to 20 MPa to less than or equal to 140 MPa, from greaterthan or equal to 30 MPa to less than or equal to 140 MPa, from greaterthan or equal to 40 MPa to less than or equal to 130 MPa, from greaterthan or equal to 50 MPa to less than or equal to 120 MPa, from greaterthan or equal to 60 MPa to less than or equal to 110 MPa, from greaterthan or equal to 60 MPa to less than or equal to 100 MPa, or fromgreater than or equal to 70 MPa to less than or equal to 90 MPa. Inother embodiments, the glass composition may have a CT from greater thanor equal to 10 MPa to less than or equal to 160 MPa, from greater thanor equal to 20 MPa to less than or equal to 160 MPa, from greater thanor equal to 30 MPa to less than or equal to 160 MPa, from greater thanor equal to 40 MPa to less than or equal to 160 MPa, from greater thanor equal to 50 MPa to less than or equal to 160 MPa, from greater thanor equal to 60 MPa to less than or equal to 160 MPa, from greater thanor equal to 70 MPa to less than or equal to 160 MPa, from greater thanor equal to 80 MPa to less than or equal to 160 MPa, from greater thanor equal to 90 MPa to less than or equal to 160 MPa, from greater thanor equal to 100 MPa to less than or equal to 160 MPa, from greater thanor equal to 110 MPa to less than or equal to 160 MPa, from greater thanor equal to 120 MPa to less than or equal to 160 MPa, from greater thanor equal to 130 MPa to less than or equal to 160 MPa, or from greaterthan or equal to 140 MPa to less than or equal to 160 MPa. In yet otherembodiments, the glass composition may have a CT from greater than orequal to 5 MPa to less than or equal to 150 MPa, from greater than orequal to 5 MPa to less than or equal to 140 MPa, from greater than orequal to 5 MPa to less than or equal to 130 MPa, from greater than orequal to 5 MPa to less than or equal to 120 MPa, from greater than orequal to 5 MPa to less than or equal to 110 MPa, from greater than orequal to 5 MPa to less than or equal to 100 MPa, from greater than orequal to 5 MPa to less than or equal to 90 MPa, from greater than orequal to 5 MPa to less than or equal to 80 MPa, from greater than orequal to 5 MPa to less than or equal to 70 MPa, from greater than orequal to 5 MPa to less than or equal to 60 MPa, from greater than orequal to 5 MPa to less than or equal to 50 MPa, from greater than orequal to 5 MPa to less than or equal to 40 MPa, from greater than orequal to 5 MPa to less than or equal to 30 MPa, from greater than orequal to 5 MPa to less than or equal to 20 MPa, or from greater than orequal to 5 MPa to less than or equal to 10 MPa.

In embodiments, the glass compositions may have a depth of compression(DOC) relative to the total thickness (t) of the glass article that isformed. In some embodiments, the DOC may be from greater than or equalto 0.05 t to less than or equal to 0.25 t, such as from greater than orequal to 0.10 t to less than or equal to 0.20 t, or greater than orequal to 0.15 t to less than or equal to 0.20 t. In other embodiments,the DOC may be from greater than or equal to 0.08 t to less than orequal to 0.25 t, greater than or equal to 0.10 t to less than or equalto 0.25 t, greater than or equal to 0.12 t to less than or equal to 0.25t, greater than or equal to 0.14 t to less than or equal to 0.25 t,greater than or equal to 0.16 t to less than or equal to 0.25 t, greaterthan or equal to 0.18 t to less than or equal to 0.25 t, greater than orequal to 0.20 t to less than or equal to 0.25 t, or greater than orequal to 0.22 t to less than or equal to 0.25 t. In still otherembodiments, the DOC may be from greater than or equal to 0.05 t to lessthan or equal to 0.22 t, greater than or equal to 0.05 t to less than orequal to 0.20 t, greater than or equal to 0.05 t to less than or equalto 0.18 t, greater than or equal to 0.05 t to less than or equal to 0.16t, greater than or equal to 0.05 t to less than or equal to 0.14 t,greater than or equal to 0.05 t to less than or equal to 0.12 t, greaterthan or equal to 0.05 t to less than or equal to 0.10 t, greater than orequal to 0.05 t to less than or equal to 0.08 t, or greater than orequal to 0.05 t to less than or equal to 0.06 t.

Compressive stress layers may be formed in the glass by exposing theglass to an ion exchange solution. In embodiments, the ion exchangesolution may be molten nitrate salt, molten phosphate salt, or a moltensulfate salt. In some embodiments, the ion exchange solution maycomprise molten KNO₃, molten NaNO₃, or combinations thereof. In someembodiments, molten LiNO₃ may be added to the molten KNO₃, molten NaNO₃,or combined molten KNO₃ and NaNO₃. In certain embodiments, the ionexchange solution may comprise about 100% molten KNO₃, about 95% moltenKNO₃, about 90% molten KNO₃, about 80% molten KNO₃, about 70% moltenKNO₃, or about 60% molten KNO₃. In certain embodiments, the ion exchangesolution may comprise about 5% molten NaNO₃, about 10% molten NaNO₃,about 20% molten NaNO₃, about 30% molten NaNO₃, or about 40% moltenNaNO₃. In other embodiments, the ion exchange solution may compriseabout 80% molten KNO₃ and about 20% molten NaNO₃, about 75% molten KNO₃and about 25% molten NaNO₃, about 70% molten KNO₃ and about 30% moltenNaNO₃, about 65% molten KNO₃ and about 35% molten NaNO₃, or about 60%molten KNO₃ and about 40% molten NaNO₃.

The glass composition may be exposed to the ion exchange solution bydipping a glass article made from the glass composition into a bath ofthe ion exchange solution, spraying the ion exchange solution onto aglass article made from the glass composition, or otherwise physicallyapplying the ion exchange solution to a glass article made from theglass composition. Upon exposure to the glass composition, the ionexchange solution may, according to embodiments, be at a temperaturefrom greater than or equal to 350° C. to less than or equal to 500° C.,such as from greater than or equal to 360° C. to less than or equal to490° C., from greater than or equal to 370° C. to less than or equal to480° C., from greater than or equal to 380° C. to less than or equal to470° C., from greater than or equal to 390° C. to less than or equal to460° C., or from greater than or equal to 400° C. to less than or equalto 420° C. In embodiments, the glass composition may be exposed to theion exchange solution for a duration from greater than or equal to 3hours to less than or equal to 48 hours, such as from greater than orequal to 8 hours to less than or equal to 44 hours, from greater than orequal to 12 hours to less than or equal to 40 hours, from greater thanor equal to 16 hours to less than or equal to 36 hours, from greaterthan or equal to 20 hours to less than or equal to 32 hours, or fromgreater than or equal to 24 hours to less than or equal to 28 hours.

In some embodiments, a two-step ion exchange process may be used toallow more control over the ion exchange profile of a strengthenedglass. In embodiments, the first step of the ion exchange may includeexposing the glass to any ion exchange solution described above, and thesecond step may include exposing the glass to any ion exchange solutiondescribed above. In some embodiments, the ion exchange solution in thefirst may be compositionally different from the ion exchange solution inthe second step. In other embodiments, the ion exchange solution in thefirst step may be compositionally the same as the ion exchange solutionin the second step. It should also be realized that, in embodiments, thetemperature and/or duration of the ion exchange in the first step may bethe same as or different from the temperature and/or duration of the ionexchange in the second step, according to various embodiments. In aparticular embodiment, in the first step, the glass composition isexposed to an ion exchange solution comprising 100% molten NaNO₃ at atemperature and for a duration described above. Subsequently, the glasscomposition is rinsed, dried, and exposed to a second ion exchangesolution comprising 100% molten KNO₃. This two-step ion exchange processmay achieve a deeper DOC and greater surface compressive stress. Theimproved ion exchange ability of Li containing aluminosilicate glassfurther enables the achievement of greater scratch resistance, increasesbearing capability, and improved vial filling line performance.

Compared to glass compositions with sodium as the only alkali or otherNa-rich glasses Li containing aluminosilicate glasses obtain improvedion exchange ability. For instance, in Li containing aluminosilicateglasses, after ion exchange, crack resistance during processing andusage is improved. With an increased amount of Li₂O in glasscompositions, greater central tension and surface compressive stress canbe obtained in relatively short time. This decreases the time used forion exchange, and saves costs in ion exchange processes.

In some embodiments, the ion exchange process may be controlled toprovide increased damage resistance to the glass composition. Thisincreased damage resistance is particularly useful when the glasscomposition is used as pharmaceutical packaging. In particular, the flawpopulation for this type of product may be uncontrolled and varieswidely with flaws being induced from initial manufacture of tubing,through the forming process, as well as subsequent handling. Glasscompositions having ion exchange profiles similar to those disclosed,and with various properties as disclosed above provide this increaseddamage resistance. The above properties and ion exchange processconditions can be used to create a spike of compression in the surfaceof the glass, which can increase the surface strength of the glass. Inembodiments where crack generation is to be limited, the stored energymay be less than or equal to about 15.00 J/m², less than or equal toabout 14.50 J/m², less than or equal to about 14.00 J/m², less than orequal to about 13.50 J/m², less than or equal to about 13.00 J/m², lessthan or equal to about 12.50 J/m², less than or equal to about 12.00J/m², less than or equal to about 11.50 J/m², less than or equal toabout 11.00 J/m², less than or equal to about 10.50 J/m², or less thanor equal to about 10.00 J/m². However, it may be desirable to increasethe stored energy in a glass composition so that when the glass cracks,multiple cracks are formed. This will allow users to better identifywhen cracks are present in the glass article formed from the glasscomposition, which may be beneficial in pharmaceutical packaging wherefractures in the glass may cause unwanted contamination. In suchembodiments, the stored energy in the glass composition is greater thanor equal to 17.00 J/m², such as greater than or equal to 18.00 J/m²,greater than or equal to 19.00 J/m², greater than or equal to 20.00J/m², greater than or equal to 21.00 J/m², greater than or equal to22.00 J/m², greater than or equal to 23.00 J/m², greater than or equalto 24.00 J/m², or greater than or equal to 26.00 J/m². In any of theabove embodiments, the stored energy may be less than or equal to 50.00J/m². The stored strain energy (Σ₀) is calculated from the followingequation:

$\Sigma_{0} = {\frac{1 - \Upsilon}{E}{\int_{{- z}*}^{z*}{\sigma^{2}dz}}}$where z* is (t/2)−d; σ is tension; E is Young's modulus; and Y isPoisson's ratio.

According to a first clause a glass pharmaceutical package has a glasscomposition comprising: from greater than or equal to 68.00 mol % toless than or equal to 81.00 mol % SiO₂; from greater than or equal to4.00 mol % to less than or equal to 11.00 mol % Al₂O₃; from greater thanor equal to 0.10 mol % to less than or equal to 16.00 mol % Li₂O; fromgreater than or equal to 0.10 mol % to less than or equal to 12.00 mol %Na₂O; from greater than or equal to 0.00 mol % to less than or equal to5.00 mol % K₂O; from greater than or equal to 0.10 mol % to less than orequal to 8.00 mol % MgO; from greater than or equal to 0.10 mol % toless than or equal to 5.00 mol % CaO; from greater than or equal to 0.00mol % to less than or equal to 0.20 mol % fining agent, wherein theglass pharmaceutical package is delamination resistant, and the glasspharmaceutical package has class 1 or class 2 chemical durability inacid, base, and water.

A second clause includes the glass pharmaceutical package according tothe first clause, wherein the glass fining agent is selected from thegroup consisting of SnO₂, CeO₂, As₂O₃, Sb₂O₃, Cl⁻, S⁻, F⁻, or Fe₂O₃.

A third clause includes the glass pharmaceutical package according toany one of the first and second clauses, wherein the glass fining agentis SnO₂.

A fourth clause includes the glass pharmaceutical package according toany one of first to third clauses, wherein the glass pharmaceuticalpackage is substantially free of at least one of B₂O₃, SrO, BaO, ZrO₂,and combinations thereof.

A fifth clause includes the glass pharmaceutical package according toany one of first to fourth clauses, wherein the glass pharmaceuticalpackage is substantially free of B₂O₃, SrO, BaO, and ZrO₂.

A sixth clause includes the glass pharmaceutical package according toany one of first to fifth clauses, wherein the glass pharmaceuticalpackage comprises from greater than or equal to 1.50 mol % to less thanor equal to 16.00 mol % Li₂O.

A seventh clause includes the glass pharmaceutical package according toany one of first to sixth clauses, wherein the glass pharmaceuticalpackage comprises from greater than or equal to 0.10 mol % to less thanor equal to 7.50 mol % MgO.

An eighth clause includes the glass pharmaceutical package according toany one of first to seventh clauses, wherein the glass pharmaceuticalpackage comprises a ratio of (Li₂O+Na₂O+K₂O)/(SiO₂+Al₂O₃) that is fromgreater than or equal to 0.05 to less than or equal to 0.50.

A ninth clause includes the glass pharmaceutical package according toany one of first to eighth clauses, wherein the glass pharmaceuticalpackage comprises a ratio of (Li₂O+Na₂O+K₂O)/(SiO₂+Al₂O₃) that is fromgreater than or equal to 0.05 to less than or equal to 0.15.

A tenth clause includes the glass pharmaceutical package according toany one of first to ninth clauses, wherein the glass pharmaceuticalpackage comprises a density from greater than or equal to 2.25 g/cm³ toless than or equal to 2.50 g/cm³.

An eleventh clause includes the glass pharmaceutical package accordingto any one of first to tenth clauses, wherein the glass pharmaceuticalpackage comprises a molar volume from greater than or equal to 24.00cm³/mol to less than or equal to 27.00 cm³/mol.

A twelfth clause includes the glass pharmaceutical package according toany one of first to eleventh clauses, wherein the glass pharmaceuticalpackage has a delamination factor less than or equal to 10.

A thirteenth clause includes the glass pharmaceutical package accordingto any one of first to twelfth clauses, wherein the glass pharmaceuticalpackage comprises a strain point from greater than or equal to 450° C.to less than or equal to 625° C.

A fourteenth clause includes the glass pharmaceutical package accordingto any one of first to thirteenth clauses, wherein the glasspharmaceutical package comprises an annealing point from greater than orequal to 500° C. to less than or equal to 675° C.

A fifteenth clause includes the glass pharmaceutical package accordingto any one of first to fourteenth clauses, wherein the glasspharmaceutical package comprises a softening point from greater than orequal to 750° C. to less than or equal to 950° C.

A sixteenth clause includes the glass pharmaceutical package accordingto any one of first to fifteenth clauses, wherein the glasspharmaceutical package comprises a CTE from greater than or equal to4.20 ppm/° C. to less than or equal to 7.00 ppm/° C.

A seventeenth clause includes the glass pharmaceutical package accordingto any one of first to sixteenth clauses, wherein the glasspharmaceutical package comprises a liquidus viscosity Log from greaterthan or equal to 3.50 poise to less than or equal to 6.00 poise.

An eighteenth clause includes the glass pharmaceutical package accordingto any one of first to seventeenth clauses, wherein the glasspharmaceutical package comprises a Young's modulus from greater than orequal to 10.00 mpsi to less than or equal to 12.00 mpsi.

A nineteenth clause includes the glass pharmaceutical package accordingto any one of first to eighteenth clauses, wherein the glasspharmaceutical package comprises a shear modulus from greater than orequal to 4.00 mpsi to less than or equal to 5.00 mpsi.

A twentieth clause includes the glass pharmaceutical package accordingto any one of first to nineteenth clauses, wherein the glasspharmaceutical package comprises a chemical durability in acid asmeasured by DIN 12116 from greater than or equal to 0.0 mg/dm² to lessthan or equal to 1.5 mg/dm².

A twenty first clause includes the glass pharmaceutical packageaccording to any one of first to twentieth clauses, wherein the glasspharmaceutical package comprises a chemical durability in acid asmeasured by DIN 12116 from greater than or equal to 0.0 mg/dm² to lessthan or equal to 0.7 mg/dm².

A twenty second clause includes the glass pharmaceutical packageaccording to any one of first to twenty first clauses, wherein the glasspharmaceutical package comprises a chemical durability in base asmeasured by ISO 695 from greater than or equal to 0 mg/dm² to less thanor equal to 175 mg/dm².

A twenty third clause includes the glass pharmaceutical packageaccording to any one of first to twenty second clauses, wherein theglass pharmaceutical package comprises a chemical durability in base asmeasured by ISO 695 from greater than or equal to 0 mg/dm² to less thanor equal to 75 mg/dm².

A twenty fourth clause includes the glass pharmaceutical packageaccording to any one of first to twenty third clauses, wherein the glasspharmaceutical package comprises a chemical durability in water asmeasured by ISO 720 from greater than or equal to 0 μg/g to less than orequal to 100 μg/g.

A twenty fifth clause includes the glass pharmaceutical packageaccording to any one of first to twenty fourth clauses, wherein theglass pharmaceutical package comprises a chemical durability in water asmeasured by ISO 720 from greater than or equal to 0 μg/g to less than orequal to 62 μg/g.

A twenty sixth clause includes the glass pharmaceutical packageaccording to any one of first to twenty fifth clauses, wherein the glasspharmaceutical package is strengthened by ion exchange and comprises asurface compressive stress of at least 350 MPa.

A twenty seventh clause includes the glass pharmaceutical packageaccording to any one of first to twenty sixth clauses, wherein the glasspharmaceutical package is strengthened by ion exchange and comprises adepth of compression from greater than or equal to 0.05 t to less thanor equal to 0.25 t.

A twenty eighth clause includes the glass pharmaceutical packageaccording to any one of first to twenty seventh clauses, wherein theglass pharmaceutical package is strengthened by ion exchange andcomprises a central tension from greater than or equal to 5 MPa to lessthan or equal to 160 MPa.

A twenty ninth clause includes the glass pharmaceutical packageaccording to any one of first to twenty eighth clauses, wherein theglass pharmaceutical package comprises a diffusivity of potassium ionsat 420° C. is from greater than or equal to 0.50 μm²/hr to less than orequal to 15.00 μm²/hr.

A thirtieth clause includes the glass pharmaceutical package accordingto any one of first to twenty ninth clauses, wherein the glasspharmaceutical package is strengthened by ion exchange and comprises astored energy of less than or equal to about 15.00 J/m².

A thirty first clause includes the glass pharmaceutical packageaccording to any one of first to thirtieth clauses, wherein the glasspharmaceutical package is strengthened by ion exchange and comprises astored energy of greater than or equal to 17.00 J/m².

A thirty second clause includes a glass pharmaceutical package having aglass composition comprising: from greater than or equal to 68.00 mol %to less than or equal to 81.00 mol % SiO₂; from greater than or equal to6.10 mol % to less than or equal to 7.00 mol % Al₂O₃; from greater thanor equal to 3.10 mol % to less than or equal to 6.60 mol % Li₂O; fromgreater than or equal to 1.40 mol % to less than or equal to 3.00 mol %Na₂O; from greater than or equal to 0.00 mol % to less than or equal to5.00 mol % K₂O; from greater than or equal to 5.10 mol % to less than orequal to 7.50 mol % MgO; from greater than or equal to 0.10 mol % toless than or equal to 5.00 mol % CaO; from greater than or equal to 0.00mol % to less than or equal to 0.20 mol % fining agent, wherein theglass pharmaceutical package is delamination resistant, the glasspharmaceutical package has class 1 or class 2 chemical durability inacid, base, and water, and the glass pharmaceutical package issubstantially free of B₂O₃, SrO, BaO, and ZrO₂.

A thirty third clause includes the glass pharmaceutical packageaccording to the thirty second clause, wherein the glass fining agent isselected from the group consisting of SnO₂, CeO₂, As₂O₃, Sb₂O₃, Cl⁻, S,F, or Fe₂O₃.

A thirty fourth clause includes the glass pharmaceutical packageaccording to any one of the thirty second and thirty third clauses,wherein the glass fining agent is SnO₂.

A thirty fifth clause includes the glass pharmaceutical packageaccording to any one of the thirty second to thirty fourth clauses,wherein the glass pharmaceutical package comprises a ratio of(Li₂O+Na₂O+K₂O)/(SiO₂+Al₂O₃) that is greater than or equal to 0.05 toless than or equal to 0.50.

A thirty sixth clause includes the glass pharmaceutical packageaccording to any one of the thirty second to thirty fifth clauses,wherein the glass pharmaceutical package a ratio of(Li₂O+Na₂O+K₂O)/(SiO₂+Al₂O₃) that is greater than or equal to 0.05 toless than or equal to 0.15.

A thirty seventh clause includes the glass pharmaceutical packageaccording to any one of the thirty second to thirty sixth clauses,wherein the glass pharmaceutical package comprises a density fromgreater than or equal to 2.25 g/cm³ to less than or equal to 2.50 g/cm³.

A thirty eighth clause includes the glass pharmaceutical packageaccording to any one of the thirty second to thirty seventh clauses,wherein the glass pharmaceutical package comprises a molar volume fromgreater than or equal to 24.00 cm³/mol to less than or equal to 27.00cm³/mol.

A thirty ninth clause includes the glass pharmaceutical packageaccording to any one of the thirty second to thirty eighth clauses,wherein the glass pharmaceutical package has a delamination factor lessthan or equal to 10.

A fortieth clause includes the glass pharmaceutical package according toany one of the thirty second to thirty ninth clauses, wherein the glasspharmaceutical package comprises a strain point from greater than orequal to 450° C. to less than or equal to 625° C.

A forty first clause includes the glass pharmaceutical package accordingto any one of the thirty second to fortieth clauses, wherein the glasspharmaceutical package comprises an annealing point from greater than orequal to 500° C. to less than or equal to 675° C.

A forty second clause includes the glass pharmaceutical packageaccording to any one of the thirty second to forty first clauses,wherein the glass pharmaceutical package comprises a softening pointfrom greater than or equal to 750° C. to less than or equal to 950° C.

A forty third clause includes the glass pharmaceutical package accordingto any one of the thirty second to forty second clauses, wherein theglass pharmaceutical package comprises a CTE from greater than or equalto 4.20 ppm/° C. to less than or equal to 7.00 ppm/° C.

A forty fourth clause includes the glass pharmaceutical packageaccording to any one of the thirty second to forty third clauses,wherein the glass pharmaceutical package comprises a liquidus viscosityLog from greater than or equal to 3.50 poise to less than or equal to6.00 poise.

A forty fifth clause includes the glass pharmaceutical package accordingto any one of the thirty second to forty fourth clauses, wherein theglass pharmaceutical package comprises a Young's modulus from greaterthan or equal to 10.00 mpsi to less than or equal to 12.00 mpsi.

A forty sixth clause includes the glass pharmaceutical package accordingto any one of the thirty second to forty fifth clauses, wherein theglass pharmaceutical package comprises a shear modulus from greater thanor equal to 4.00 mpsi to less than or equal to 5.00 mpsi.

A forty seventh clause includes the glass pharmaceutical packageaccording to any one of the thirty second to forty sixth clauses,wherein the glass pharmaceutical package comprises a chemical durabilityin acid as measured by DIN 12116 from greater than or equal to 0.0mg/dm² to less than or equal to 1.5 mg/dm².

A forty eighth clause includes the glass pharmaceutical packageaccording to any one of the thirty second to forty seventh clauses,wherein the glass pharmaceutical package comprises a chemical durabilityin acid as measured by DIN 12116 from greater than or equal to 0.0mg/dm² to less than or equal to 0.7 mg/dm².

A forty ninth clause includes the glass pharmaceutical package accordingto any one of the thirty second to forty eighth clauses, wherein theglass pharmaceutical package comprises a chemical durability in base asmeasured by ISO 695 from greater than or equal to 0 mg/dm² to less thanor equal to 175 mg/dm².

A fiftieth clause includes the glass pharmaceutical package according toany one of the thirty second to forty ninth clauses, wherein the glasspharmaceutical package comprises a chemical durability in base asmeasured by ISO 695 from greater than or equal to 0 mg/dm² to less thanor equal to 75 mg/dm².

A fifty first clause includes the glass pharmaceutical package accordingto any one of the thirty second to fiftieth clauses, wherein the glasspharmaceutical package comprises a chemical durability in water asmeasured by ISO 720 from greater than or equal to 0 μg/g to less than orequal to 100 μg/g.

A fifty second clause includes the glass pharmaceutical packageaccording to any one of the thirty second to fifty first clauses,wherein the glass pharmaceutical package comprises a chemical durabilityin water as measured by ISO 720 from greater than or equal to 0 μg/g toless than or equal to 62 μg/g.

A fifty third clause includes the glass pharmaceutical package accordingto any one of the thirty second to fifty second clauses, wherein theglass pharmaceutical package is strengthened by ion exchange andcomprises a surface compressive stress of at least 350 MPa.

A fifty fourth clause includes the glass pharmaceutical packageaccording to any one of the thirty second to fifty third clauses,wherein the glass pharmaceutical package comprises is strengthened byion exchange and a depth of compression from greater than or equal to0.05 t to 0.25 t.

A fifty fifth clause includes the glass pharmaceutical package accordingto any one of the thirty second to fifty fourth clauses, wherein theglass pharmaceutical package is strengthened by ion exchange andcomprises a central tension from greater than or equal to 5 MPa to lessthan or equal to 160 MPa.

A fifty sixth clause includes the glass pharmaceutical package accordingto any one of the thirty second to fifty fifth clauses, wherein theglass pharmaceutical package comprises a diffusivity of potassium ionsat 420° C. is from greater than or equal to 0.50 μm²/hr to less than orequal to 15.00 μm²/hr.

A fifty seventh clause includes the glass pharmaceutical packageaccording to any one of the thirty second to fifty sixth clauses,wherein the glass pharmaceutical package is strengthened by ion exchangeand comprises a stored energy of less than or equal to about 15.00 J/m².

A fifty eighth clause includes the glass pharmaceutical packageaccording to any one of the thirty second to fifty seventh clauses,wherein the glass pharmaceutical package is strengthened by ion exchangeand comprises a stored energy of greater than or equal to 17.00 J/m².

EXAMPLES

Embodiments will be further clarified by the following examples. Itshould be understood that these examples are not limiting to theembodiments described above.

Example 1

Glass Samples 1-38 were formed from compositions provided in TABLE 1below. The glasses having compositions as listed in TABLE 1 below weremade from batches of conventional source or starting materials and weremelted in a platinum crucible at temperatures from 1570° C. to 1650° C.in air with an aluminum cover.

TABLE 1 mol % Sample SiO₂ Al₂O₃ Na₂O K₂O MgO CaO SnO₂ Li₂O 1 76.3 6.49.8 0.03 5.4 0.2 0.2 1.7 2 76.5 6.4 7.9 0.02 5.3 0.2 0.2 3.6 3 76.3 6.45.9 0.02 5.4 0.2 0.2 5.6 4 76.4 6.4 3.9 0.02 5.3 0.2 0.2 7.5 5 76.3 6.42.0 0.03 5.3 0.2 0.2 9.5 6 76.7 6.5 2.1 0.03 4.9 0.2 0.2 9.5 7 74.2 6.34.0 0.03 5.3 0.2 0.2 9.7 8 78.1 6.4 4.0 0.02 5.3 0.2 0.2 5.8 9 76.2 4.44.0 0.03 5.3 0.2 0.2 9.7 10 76.3 8.3 4.0 0.03 5.4 0.2 0.2 5.7 11 76.26.4 4.0 2.04 5.3 0.2 0.2 5.6 12 76.2 6.4 3.9 4.02 5.3 0.2 0.2 3.7 1376.3 6.3 4.0 0.08 3.3 0.2 0.2 9.6 14 76.3 6.4 4.0 0.04 7.2 0.2 0.2 5.715 76.2 6.4 4.0 0.04 5.4 2.0 0.2 5.7 16 76.1 6.5 3.9 0.04 5.3 4.1 0.23.8 17 74.8 6.5 2.0 0.02 4.8 0.2 0.2 11.5 18 78.3 6.3 2.0 0.01 5.3 0.20.2 7.7 19 76.7 4.5 2.0 0.01 5.1 0.2 0.2 11.4 20 76.2 8.4 2.0 0.01 5.40.2 0.2 7.6 21 76.4 6.4 1.9 1.93 5.2 0.2 0.2 7.7 22 76.5 6.3 1.9 3.985.2 0.2 0.2 5.7 23 76.2 6.4 2.0 0.04 3.2 0.2 0.2 11.7 24 76.0 6.4 2.00.03 7.4 0.1 0.2 7.8 25 76.3 6.4 2.0 0.03 5.2 2.1 0.2 7.7 26 76.4 6.42.0 0.03 5.3 4.0 0.2 5.7 27 78.2 6.3 2.0 2.03 5.3 0.2 0.2 5.8 28 78.26.3 2.0 1.04 5.4 1.1 0.2 5.7 29 78.3 6.4 2.0 0.03 5.3 2.1 0.2 5.7 3076.2 8.3 2.0 2.00 5.3 0.2 0.2 5.8 31 76.3 8.4 2.0 1.03 5.4 1.2 0.2 5.632 76.2 8.4 1.9 0.04 5.5 2.2 0.2 5.5 33 76.7 6.2 1.0 1.93 5.1 0.2 0.28.7 34 76.7 6.2 3.0 2.02 5.1 0.2 0.2 6.6 35 76.7 6.1 2.0 1.01 5.1 0.20.2 8.7 36 76.8 6.1 2.0 2.91 5.2 0.2 0.2 6.6 37 76.6 6.2 5.9 1.98 5.20.1 0.2 3.6 38 76.8 6.2 1.0 0.99 5.1 0.2 0.2 9.5

Various measured properties of Samples 1-38 are provided below in TABLE2.

TABLE 2 ISO DIN ISO 720 12116 695 Log μg (acid) (base) (viscosity Temp.Na₂O Mean of Mean Liquidus at at CTE SOC per half of Strain AnnealingSoftening Temp. liquidus) 35000 (RT- nm/ gram mass mass Point PointPoint Internal Log Poise 300° C.) mm/ glass loss loss Sample ° C. ° C. °C. ° C. (poise) ° C. ppm/° C. Mpa tested mg/dm² mg/dm² 1 547 600 8611070 5.5 1200 6.9 3.1 56 −0.4 −60 2 529 579 841 1070 5.2 1169 6.5 3.1 54−0.3 −59 3 519 567 819 1095 4.9 1147 6.2 3.0 52 −0.4 −58 4 516 564 8121090 4.9 1136 5.6 2.9 55 −0.4 −56 5 513 561 NA 5.5 52 −0.3 −58 6 518 565NA 1140 4.5 1130 5.6 2.9 7 490 534 763 1045 4.7 1065 6.5 2.9 73 −0.5 −568 554 606 NA 1170 4.9 1224 5.1 3.1 50 −0.5 −54 9 472 515 737 1095 4.31048 6.4 2.9 92 −0.3 −57 10 591 642 NA 1195 4.9 1248 5.3 3.0 47 −0.4 −4611 517 567 822 1080 5.1 1163 6.5 3.0 52 −0.3 −53 12 530 581 849 10655.50 1204 6.9 3.0 52 −0.4 −64 13 484 529 770 1020 5.0 1087 6.3 2.9 74−0.4 −52 14 558 608 879 1220 4.3 1180 5.4 3.0 55 −0.3 −59 15 540 589 8461095 5.0 1161 5.5 3.0 57 −0.3 −52 16 577 625 875 1145 4.9 1198 5.4 3.043 −0.5 −51 17 496 539 761 1135 4.1 1064 6.0 2.8 66 −0.4 −51 18 553 604NA 1185 4.7 1203 5.0 3.0 42 −0.4 −43 19 477 520 NA 1165 3.8 1045 6.3 2.976 −0.3 −41 20 590 639 NA 1215 4.6 1227 4.9 3.0 41 −0.4 −46 21 517 566818 1105 4.9 1153 6.0 2.9 42 −0.4 −48 22 525 575 836 1065 5.3 1180 6.02.9 49 −0.4 −53 23 490 534 NA 6.0 2.9 67 −0.4 −51 24 556 605 NA 1210 4.31173 5.1 2.9 50 −0.3 −45 25 539 586 NA 1130 4.7 1149 5.1 2.9 53 −0.4 −4426 570 616 NA 1185 4.5 1176 4.9 2.9 48 −0.4 −43 27 560 611 879.1 11705.0 1236 5.3 3.0 39 −57 28 567 618 893.9 1160 5.0 1233 5.0 3.0 40 −52 291225 4.6 1231 38 −52 30 1205 4.9 1260 45 −61 31 599 651 NA 1185 5.0 12514.9 3.0 43 −57 32 613 664 932.1 1170 5.1 1247 4.5 3.0 46 −0.4 −56 33 518565 NA 1095 4.9 1141 5.7 47 −0.4 −55 34 515 564 826.2 1095 4.9 1155 6.348 −0.4 −56 35 517 564 NA 1090 4.9 1138 5.7 50 −0.4 −54 36 519 567 824.51095 5.0 1162 6.1 47 −0.4 −57 37 522 574 836.8 1050 5.5 1182 6.7 51 −0.4−56 38 520 567 NA 1160 4.4 1129 5.5 54 −0.3 −53

The compositions of glasses of Comparative Samples C1-C21 are providedin TABLE 3 below.

TABLE 3 mol % Sample SiO₂ Al₂O₃ Na₂O K₂O MgO CaO SnO₂ Li₂O C1  70.4 5.43.5 0.0 5.1 0.0 0.2 15.5 C2  68.7 9.7 6.7 0.0 4.8 0.0 0.2 9.9 C3  74.75.8 9.0 0.0 5.2 0.0 0.2 5.0 C4  76.5 6.4 11.5 0.03 5.3 0.1 0.2 0.0 C5 74.4 6.4 0.0 0.02 5.1 0.2 0.2 13.6 C6  78.2 6.4 0.0 0.03 5.3 0.1 0.2 9.6C7  77.2 4.4 0.0 0.03 4.5 0.2 0.2 13.5 C8  76.4 8.4 0.0 0.03 5.2 0.2 0.29.6 C9  75.9 6.5 0.0 1.99 5.6 0.2 0.2 9.6 C10 76.4 6.4 0.0 3.95 5.3 0.20.2 7.6 C11 76.1 6.4 0.0 0.04 3.4 0.2 0.2 13.7 C12 76.3 6.3 0.0 0.03 7.20.2 0.2 9.8 C13 76.1 6.4 0.0 0.03 5.4 2.1 0.2 9.7 C14 76.5 6.3 0.0 0.035.3 4.0 0.2 7.6 C15 80.5 6.3 0.0 2.01 5.2 0.2 0.2 5.6 C16 80.4 6.3 0.01.01 5.2 1.1 0.2 5.7 C17 80.5 6.2 0.0 0.03 5.3 2.1 0.2 5.6 C18 76.4 10.20.0 1.99 5.4 0.2 0.2 5.5 C19 76.5 10.3 0.0 0.99 5.3 1.1 0.2 5.6 C20 76.410.4 0.0 0.03 5.2 2.1 0.2 5.6 C21 76.3 6.4 0.0 0.02 5.4 0.2 0.2 11.5

Various measured properties of Comparative Samples C1-C21 are providedbelow in TABLE 4.

TABLE 4 ISO DIN ISO 720 12116 695 Log μg (acid) (base) (viscosity Temp.Na₂O Mean of Mean Liquidus at at CTE SOC per half of Strain AnnealingSoftening Temp. liquidus) 35000 (RT- nm/ gram mass mass Point PointPoint Internal Log Poise 300° C.) mm/ glass loss loss Sample ° C. ° C. °C. ° C. (poise) ° C. ppm/° C. Mpa tested mg/dm² mg/dm² C1  153 −0.4 −72C2  105 −0.4 −66 C3  80 −0.5 −59 C4  595 648 905 1040 6.6 1222 6.9 3.168 −0.4 −68 C5  504 547 NA 5.6 2.8 64 −0.4 −50 C6  563 612 NA 1155 4.51142 4.5 3.0 50 −51 C7  488 529 NA 6.0 2.8 69 −58 C8  595 644 NA 4.6 3.075 −54 C9  524 571 827 1250 4.2 1189 5.6 3.0 46 −58 C10 528 575 823 5.92.9 71 −0.4 −43 C11 501 546 NA 5.5 2.8 67 −0.4 −49 C12 561 608 NA 12653.9 1161 4.6 2.9 57 −0.4 −48 C13 544 590 NA 1235 4.0 1138 4.6 2.9 52−0.4 −38 C14 569 615 NA 1275 3.9 1163 4.6 2.9 54 −0.3 −46 C15 1285 4.71304 30 −54 C16 1255 4.9 1304 30 −59 C17 >1295 <4.6 1298 31 −54 C18 12405.1 1317 38 −69 C19 1255 4.9 1303 40 −66 C20 1285 4.6 1292 37 −62 C21530 576 NA 1230 3.9 1120 5.2 2.9 51 −0.3 −56

In the above samples, the amount of Li₂O in the glass is increased inSamples 1-6 (as shown in Table 1), where Comparative Sample 4 is used asa control without Li₂O, and the physical properties of various sampleglasses are shown in FIG. 3A-FIG. 3G. With the increase in Li₂O contentit was observed that: as shown in FIG. 3A, which is a plot of densityand molar volume versus Na₂O mol %, density decreases as the amount ofLi₂O increases (it should be noted that in FIG. 3A-FIG. 3G the amount ofLi₂O has a negative correlation with the amount of Na₂O, such that inthese figures higher amounts of Na₂O indicate lower amounts of Li₂O andvice versa); as also shown in FIG. 3A, the molar volume decreaseslinearly as Li₂O increases, which can be used to predict molar volume aswell as density for other compositions; as shown in FIG. 3B, which is aplot of SOC versus Na₂O mol %, SOC decreases linearly as the amount ofLi₂O increases, which relates with elastic modulus and atomic bonding inthe glass network; as shown in FIG. 3C, which is a plot of annealingpoint, strain point, and softening point versus Na₂O mol %, the strainpoint, annealing point, and softening temperature all generally decreaseas Li₂O is added, but as shown in FIG. 3C these properties all reachminimum points where the amount of Na₂O is about 4 mol %, showing thatmerely adding Li₂O is not sufficient; as shown in FIG. 3D, which is aplot of CTE versus Na₂O mol %, CTE <300° C. on heating decreaseslinearly with an increase in the amount of Li₂O, which can also be usedto predict CTE for other compositions; liquidus temperature alsoincreases greatly with small additions of Li₂O as shown in FIG. 3E,which is a plot of liquidus temperature versus Na₂O mol %; as shown inFIG. 3F, which is a plot of heat flow (where Exo means exotherm) plottedby Na₂O mol % versus temperature, primary crystallization phases atliquidus temperature evolve from protoenstatite (MgSiO₃, when Na₂O>4 mol%) to spodumene (LiAl(SiO₃)₂ when Na₂O<4 mol %), crystallizationtendency increases with the exothermic activity as shown by DSCmeasurements in FIG. 3F, and the main crystalline phase is lithiumaluminum silicate LiAl(SiO₃)₂ and is more clearly defined as the amountof lithium increases; as shown in FIG. 3G, which is a plot of Young'smodulus, shear modulus, and Poisson's ratio versus Na₂O mol %, Young'smodulus, shear modulus, and Poisson's Ratio increase when Li₂O is addedin amounts over 5 mol %.

The durability of glasses of Samples 1-6 was also tested for chemicaldurability in acid, a base, and water (hydrolytic durability) accordingto DIN 12116, ISO 695, and ISO 720, respectively, where ComparativeExample 4 is a non-Li₂O containing control sample. As shown in FIG. 4A,which is a plot of DIN 12116, ISO 695 and ISO 720 results versus Na₂Omol %, Samples 1-6 all show improved chemical durability thanComparative Sample 4. With the initial replacement of Na₂O with Li₂O,hydrolytic and base durability improve dramatically, and there is aslight improvement in acid durability. FIG. 4B, which is a plot of ionconcentration in ISO 720 versus Na₂O, shows the absolute ionconcentrations in ISO 720 solutions measured by ICP-MS. FIG. 4C, whichis a plot of ion concentrations versus Na₂O mol %, shows normalizedleached ion concentrations measured on the solutions recovered from theISO 720 test, and it shows that Li⁺ and Ca₂ ⁺ are preferentially leachedout from the glass network, and Li⁺ and Ca²⁺ preferentially leached outfrom an Na-rich composition than from a Li-rich composition.

Additional glass compositions were adjusted by fixing the Na₂O mol % at4 mol % (Samples 7 to 16), fixing the Na₂O mol % at 2 mol % (Samples 17to 26), and comparing them to glass samples with the Na₂O mol % at 0 mol% (Comparative Samples 5 to 14), and fixing Li₂O mol % at 5.6 mol % andfixing MgO at 5.3 mol % (Samples 27 to 32 and Comparative Samples 14 to19). Composition adjustments are listed in TABLES 1 and 3 above.Physical properties as well as chemical durability were measured andlisted in TABLES 2 and 4 above.

By varying the amounts of SiO₂, Al₂O₃, MgO, CaO, and K₂O, theLi-containing glass composition of various samples were able to lowerthe crystallization tendency of the glass as shown by the softeningtemperatures measured by PPV (e.g., Samples 7, 9, 11-17, 21, 22, 27, 28,and 32); improving properties for glass processing, (e.g., temperaturefor viscosity at 35000 poise is above liquidus temperature and alsobelow 1200° C. for tube forming and vial making (e.g., examples 7,11-13, 15, 16, 18, 21, 22, and 25); improving chemical durability inacid by DIN 12116 (class S1, half the mass loss per unit area of totalsurface of the glass, in mg/dm², 0 to 0.7 mg/dm²), in a base by ISO 695(class Al, mass loss per unit area of total surface of the glass, inmg/dm², up to 75 mg/dm²), and in water by ISO 720 (HGA1, equivalent ofalkali expressed as mass of Na₂O per gram of glass grains, in μg/g, upto and including 62 μg/g)—e.g., Samples 8, 10-12, 14, 15, 16, 18, 20-22,24, 25, 26, and 27-32; and samples with particularly lowercrystallization tendency, preferred properties for glass processing, andgood chemical durability before ion exchange are Samples 1-4, 11, 12,15, 16, 21 and 22.

FIG. 5 , which is a plot of ISO 720 results versus the ratio of alkalimetals to network forming components, shows that ISO 720 resultschanging (Li₂O+Na₂O+K₂O)/(SiO₂+Al₂O₃) ratio for glasses in thisdisclosure, with an increase in alkali contents, hydrolytic chemicaldurability decreases. FIG. 6 , which is a plot of ISO 720 results versussoftening points, shows the hydrolytic chemical durability by ISO 720 ofvarious glasses changing with the glass softening temperatures. FIG. 6shows that when glass composition (solid squares) transiting fromLi-free and B-free aluminosilicate glasses (solid diamonds) towards Type1B borosilicate glasses (solid triangle), softening temperature greatlydecreases and hydrolytic chemical durability improves. However, forborosilicate glasses, there is delamination probability of innersurfaces when contacting with aqueous solutions (e.g., pharmaceuticalsolutions). FIG. 6 indicates that by introducing Li₂O in glasscomposition, it is possible to get properties similar to B-freealuminosilicate glasses close to a Type 1B borosilicate without theaddition of boron. Thus, improving physical properties for tubereforming without delamination problems for chemical durability.

The ion exchange ability of Li containing glass compositions are alsoshown in the samples and comparative samples. After ion exchange, crackresistance during processing and usage is improved. FIG. 7A to FIG. 7C,which are plots of CT, CS, DOL_(k) versus duration of ion exchangetreatment for Samples C4, 1, 2, 3, 4, and 6, show the properties of ionexchange ability varied with glass composition. With an increase in theamount of Li₂O in the glass composition (Li₂O increases from Sample 1 toSample 6), greater central tension and surface compressive stress can beobtained in relatively short time. TABLE 5 shows the glass sample, ionexchange temperature and duration of the ion exchange for glass samplesexposed to an ion exchange solution comprising 70 wt % KNO₃ and 30 wt %NaNO₃. The CT, stored energy, compressive stress, and DOL_(k) of thesamples are also given in TABLE 5.

TABLE 5 Ion Ion Exchange Exchange Temperature Durations CT SSE/area CSSample (° C.) (hrs) (MPa) (J/m²) (MPa) DOL_(k) (μm) 1 450 18 65.2 13.5345 16.0 2 420 12 38.9 6.0 415 20.0 2 480 6 32.9 3.6 372 30.8 3 420 1849.4 9.0 412 17.2 3 450 12 45.3 7.0 404 21.0 3 480 6 40.9 6.0 369 23.5 4450 6 67.0 13.0 423 11.0 11 480 6 50.1 9.2 391 20.6 12 420 18 72.2 15.7405 10.7 15 480 6 53.5 9.4 405 17.3 16 420 18 61.1 12.4 366 13.7 16 4506 53.2 9.9 328 12.1 21 420 18 60.4 14.6 390 18.5 21 450 12 61.5 14.6 36023.4 21 480 6 54.2 10.6 319 27.8

TABLE 6 shows the glass sample, ion exchange temperature and duration ofthe ion exchange for glass samples exposed to an ion exchange solutioncomprising 95 wt % KNO₃ and 5 wt % NaNO₃. The CT, stored energy,compressive stress and DOL_(k) of the samples are also given in TABLE 6.

TABLE 6 Ion Ion Exchange Exchange Temperature Durations CT SSE/area CSSample (° C.) (hrs) (MPa) (J/m²) (MPa) DOL_(k) (μm) 1 420 24 25.8 4.3571 40.4 2 420 12 23.7 2.5 582 21.4 3 420 18 28.9 3.3 571 18.6

FIG. 8A and FIG. 8B, which are plots of CT versus duration of the ionexchange treatment performed on glass Samples 6 and 7, respectively,show the effects of different salt bath type on CT, for high Li₂Ocontaining glasses (e.g., Samples 6 and 7), there is little effect ofsalt bath type with NaNO₃>30 wt % on CT.

FIG. 9A to FIG. 9D are ion exchange profiles for a glass composition ofSample 7 in various ion exchange solutions. FIG. 9A is an ion exchangesolution of 70 wt % KNO₃ and 30 wt % NaNO₃ at 420° C.; FIG. 9B is an ionexchange solution of 30 wt % KNO₃ and 70 wt % NaNO₃ at 420° C.; FIG. 9Cis an ion exchange solution of 100 wt % NaNO₃ at 420° C.; and FIG. 9D isan ion exchange solution of 100 wt % NaNO₃ at 450° C. These ion exchangeprofiles show the effects of ion exchange solution type, ion exchangetemperature, and ion exchange duration on stress profile in the glass.For example, after short ion exchange duration (e.g., 6 hours) at 420°C., Sample 7 treated in mixed salt bath (FIG. 9A and FIG. 9B) hasrelatively smaller positive area under stress profile than glass treatedin 100% NaNO₃ (FIG. 9C). After the same ion exchange time duration,greater CT was obtained at higher ion exchange temperature (450° C.,FIG. 9D) than CT for glass treated at lower temperature (420° C., FIG.9C).

FIG. 10 , which is a plot of ISO 720 results versus Na₂O mol %, showsthat the hydrolytic chemical durability (ISO 720) of Li-containingaluminosilicate glasses is greatly improved by the ion exchange process.The hydrolytic chemical durability of Comparative Sample 4 is improvedfrom 68 μg/g (on the border line of class HGA1) to 37 μg/g by ionexchange, and the hydrolytic chemical durability of Li-containingglasses get down to below 30 μg/g. Thus, FIG. 10 shows that when Li₂O isadded beyond a certain amount, the advantages of adding Li₂O diminish.FIG. 11A to FIG. 11D, which are plots of ion concentrations in ISO 720solutions versus Na₂O mol %, show the ion concentration and normalizedleach ion concentrations in ISO 720 solutions by ICP-MS analysis forglasses before and after ion exchange. After ion exchange, Li, Ca, andAl cations leached into solution are much less than glass as-made (FIG.11B, FIG. 11C, and FIG. 11D).

The ion exchange process greatly reduces the amount of Li, Ca, and Alcations leached out from glass into solution (as shown in FIG. 11B, FIG.11C, and FIG. 11D). The structure on the glass surface is condensedafter ion exchange through lithium exchanged for sodium or potassium,which reduces the overall dissolution rates of ions as well as glass, sothe hydrolytic resistance of ion exchanged glasses is much better thanthat of the as-made glasses (FIG. 10 ).

FIG. 12A and FIG. 12B, which are plots of ion concentrations versusdissolution time, shows one example of the dissolution kinetics studyfor glasses before ion exchange. Glasses having compositions of Samples1-7 and Comparative Sample 4 with dimension of 25.47 mm×25.47 mm×1 mmwere immersed in 200 ml DI H₂O at 95° C. for 5 weeks. At each timeinterval, 2 mL solutions were taken and analyzed by ICP-MS, thenrefilled with 2 mL DI water. FIG. 12A shows the Si concentration (ppm)measured by ICP-MS and linear fitted with R₂>0.98 for Samples C4, 1, 2,4, and 6. FIG. 12B shows the dissolution rate of Si (ppm/hour) changedwith glass composition (Na₂O mol %). The trend of dissolution rate of Siis consistent with the results of standard tests shown in FIG. 4A. ForComparative Sample 4 and Samples 1-7, the dissolution kinetics of glassnetwork former (Si) shows linear time dependence. The dissolution ratesof glass network former (Si) show linear composition dependence on Na₂Ocontent for Samples 1, 2, 4, 6, and 7).

Example 2

Various glass samples as formed above in Example 1 were subjected to ionexchange to examine the diffusivity of potassium under various ionexchange conditions. TABLE 7 shows the glass sample, ion exchangesolution used, and ion exchange temperature used for this example. Thediffusivity of potassium at the various ion exchange conditions is alsogiven in TABLE 7.

TABLE 7 Salt Bath (wt %) Diffusivity (μm²/hr) Sample KNO₃ NaNO₃ 420° C.450° C. 480° C. 1 95 5 9.38 2 95 5 4.81 3 95 5 2.54 4 95 5 1.40 6 95 50.77 C4 95 5 1.46 1 70 30 7.90 33.85 2 70 30 3.86 8.28 19.49 3 70 302.10 4.65 11.86 4 70 30 1.48 2.82 8.15 6 70 30 0.68 5.09 C4 70 30 18.2811 70 30 1.94 3.78 9.01 12 70 30 2.68 15 70 30 1.13 2.56 6.46 16 70 301.23 3.34 21 70 30 2.63 5.91 13.51 1 50 50 6.78 2 50 50 3.45 3 50 502.06 4 50 50 1.13 6 50 50 0.66 C4 50 50 15.80 1 30 70 5.52 2 30 70 2.653 30 70 1.46 4 30 70 0.86 C4 30 70 12.84

Example 3

The effect of alkali distribution on hydrolytic and basic durability inaccordance with ISO 720 and ISO 695, respectively was determined forvarious samples of the glasses formed in accordance with Example 1. Thesamples used in this example all had a total alkali metal amount of11.69 mol %. Within this total alkali metal content of 11.69 mol %,samples were selected where the amount of lithium relative to the totalamount of alkali metal, the amount of sodium relative to the totalamount of alkali metal, and the amount of potassium relative to thetotal amount of alkali metal was different. The hydrolytic and basicdurability of the glass was measured for each of these samples. Theresults of the hydrolytic durability according to ISO 720 is shown inthe triangular plot of FIG. 15 , and the results of the basic chemicaldurability according to ISO 695 is shown in the triangular plot of FIG.16 . As shown in FIGS. 15 and 16 , samples having about 66% lithiumrelative to the total amount of alkali metal, about 17% sodium relativeto the total amount of alkali metal, and about 17% of potassium relativeto the total amount of alkali metal showed the best durability in bothwater and base.

Example 4

A Li₂O containing glass was ion-exchanged in a mixed molten salt bathcomprising 80% KNO₃ and 20% NaNO₃. FIG. 2 shows the SCALP data of thestress associated with sodium ion concentration. The ion exchange alsoyielded a ‘spike’ of compression at the surface of the glass, with avalue of 675 MPa and a DOL_(k) of 19 μm. The ability to provide a thinlayer of high compression increases the load bearing capability of thepart allowing it to perform better against random, high level, stressevents that can occur on the manufacturing line. FIG. 13 shows a pictureof a 50×50×1.1 mm thick part ion-exchanged using this particularschedule, after poke testing with a sharp WC tip. The part breaks intoonly 2 parts, consistent with the stored strain energy/area (SSE/area)of 13.9 J/m². The SSE/area can also be tuned to yield a more fragmentedbreak pattern, as shown in FIG. 14 . The stress profile parametersassociated with this condition (23 hour ion exchange duration) are shownin TABLE 8 below.

TABLE 8 Ion Exchange CT SSE/area DOC CS DOL_(k) Duration (hrs) (MPa)(J/m²) (μm) (MPa) (μm) 16 98.70 33.13 222 693.6 12.2 23 83.29 24.18 217674.5 15.0 32 67.10 16.02 208 639.2 18.3

It will be apparent to those skilled in the art that variousmodifications and variations can be made to the embodiments describedherein without departing from the spirit and scope of the claimedsubject matter. Thus it is intended that the specification cover themodifications and variations of the various embodiments described hereinprovided such modification and variations come within the scope of theappended claims and their equivalents.

What is claimed is:
 1. A glass pharmaceutical package having a glasscomposition comprising: from greater than or equal to 68.00 mol % toless than or equal to 81.00 mol % SiO₂; from greater than or equal to4.00 mol % to less than or equal to 11.00 mol % Al₂O₃; from greater thanor equal to 0.10 mol % to less than or equal to 16.00 mol % Li₂O; fromgreater than or equal to 0.10 mol % to less than or equal to 12.00 mol %Na₂O; from greater than or equal to 0.00 mol % to less than or equal to5.00 mol % K₂O; from greater than or equal to 0.10 mol % to less than orequal to 8.00 mol % MgO; from greater than or equal to 0.10 mol % toless than or equal to 5.00 mol % CaO; from greater than or equal to 0.00mol % to less than or equal to 0.20 mol % fining agent, wherein theglass pharmaceutical package is delamination resistant, the glasspharmaceutical package has class 1 or class 2 chemical durability inacid, base, and water, and the glass pharmaceutical package isstrengthened by ion exchange and comprises: a surface compressive stressof at least 350 MPa; a central tension from greater than or equal to 5MPa to less than or equal to 160 MPa; and a depth of compression fromgreater than or equal to 0.05t to less than or equal to 0.25t.
 2. Theglass pharmaceutical package according to claim 1, wherein the glasspharmaceutical package comprises from greater than or equal to 1.50 mol% to less than or equal to 16.00 mol % Li₂O.
 3. The glass pharmaceuticalpackage according to claim 1, wherein the glass pharmaceutical packagecomprises from greater than or equal to 0.10 mol % to less than or equalto 7.50 mol % MgO.
 4. The glass pharmaceutical package according toclaim 1, wherein the glass composition comprises greater than 0.00 mol %of the fining agent, and the fining agent is selected from the groupconsisting of SnO₂, CeO₂, As₂O₃, Sb₂O₃, Cl⁻, S⁻, F⁻, or Fe₂O₃.
 5. Theglass pharmaceutical package according to claim 4 wherein the finingagent consists of SnO₂.
 6. The glass pharmaceutical package according toclaim 1, wherein the glass pharmaceutical package is substantially freeof at least one of B₂O₃, SrO, BaO, and ZrO₂.
 7. The glass pharmaceuticalpackage according to claim 1, wherein the glass pharmaceutical packageis substantially free of B₂O₃, SrO, BaO, and ZrO₂.
 8. The glasspharmaceutical package according to claim 1, wherein the glasspharmaceutical package comprises a ratio of (Li₂O+Na₂O+K₂O)/(SiO2+Al₂O₃)that is from greater than or equal to 0.05 to less than or equal to0.50.
 9. The glass pharmaceutical package according to claim 1, whereinthe glass pharmaceutical package comprises a ratio of(Li₂O+Na₂O+K₂O)/(SiO₂+Al₂O₃) that is from greater than or equal to 0.05to less than or equal to 0.15.
 10. The glass pharmaceutical packageaccording to claim 1, wherein the glass pharmaceutical package comprisesa density from greater than or equal to 2.25 g/cm³ to less than or equalto 2.50 g/cm³.
 11. The glass pharmaceutical package according to claim1, wherein the glass pharmaceutical package comprises a molar volumefrom greater than or equal to 24.00 cm³/mol to less than or equal to27.00 cm³/mol.
 12. The glass pharmaceutical package according to claim1, wherein the glass pharmaceutical package has a delamination factorless than or equal to
 10. 13. The glass pharmaceutical package accordingto claim 1, wherein the glass composition comprises a strain point fromgreater than or equal to 450° C. to less than or equal to 625° C. 14.The glass pharmaceutical package according to claim 1, wherein the glasscomposition comprises an annealing point from greater than or equal to500° C. to less than or equal to 675° C.
 15. The glass pharmaceuticalpackage according to claim 1, wherein the glass composition comprises asoftening point from greater than or equal to 750° C. to less than orequal to 950° C.
 16. The glass pharmaceutical package according to claim1, wherein the glass composition comprises a coefficient of thermalexpansion (CTE) from greater than or equal to 4.20 ppm/° C. to less thanor equal to 7.00 ppm/° C.
 17. The glass pharmaceutical package accordingto claim 1, wherein the glass composition comprises a Log of liquidusviscosity from greater than or equal to 3.50 poise to less than or equalto 6.00 poise.
 18. The glass pharmaceutical package according to claim1, wherein the glass composition comprises a Young's modulus fromgreater than or equal to 10.00 mpsi to less than or equal to 12.00 mpsi.19. The glass pharmaceutical package according to claim 1, wherein theglass composition comprises a shear modulus from greater than or equalto 4.00 mpsi to less than or equal to 5.00 mpsi.
 20. The glasspharmaceutical package according to claim 1, wherein the glasspharmaceutical package comprises a chemical durability in acid asmeasured by DIN 12116 from greater than or equal to 0.0 mg/dm² to lessthan or equal to 1.5 mg/dm².
 21. The glass pharmaceutical packageaccording to claim 1, wherein the glass pharmaceutical package comprisesa chemical durability in acid as measured by DIN 12116 from greater thanor equal to 0.0 mg/dm² to less than or equal to 0.7 mg/dm².
 22. Theglass pharmaceutical package according to claim 1, wherein the glasspharmaceutical package comprises a chemical durability in base asmeasured by ISO 695 from greater than or equal to 0 mg/dm² to less thanor equal to 175 mg/dm².
 23. The glass pharmaceutical package accordingto claim 1, wherein the glass pharmaceutical package comprises achemical durability in base as measured by ISO 695 from greater than orequal to 0 mg/dm² to less than or equal to 75 mg/dm².
 24. The glasspharmaceutical package according to claim 1, wherein the glasspharmaceutical package comprises a chemical durability in water asmeasured by ISO 720 from greater than or equal to 0 μg/g to less than orequal to 100 μg/g.
 25. The glass pharmaceutical package according toclaim 1, wherein the glass pharmaceutical package comprises a chemicaldurability in water as measured by ISO 720 from greater than or equal to0 μg/g to less than or equal to 62 μg/g.
 26. The glass pharmaceuticalpackage according to claim 1, wherein the glass pharmaceutical packagecomprises a diffusivity of potassium ions at 420° C. from greater thanor equal to 0.50 μm²/hr to less than or equal to 15.00 μm²/hr.
 27. Theglass pharmaceutical package according to claim 1, wherein the glasspharmaceutical package comprises a stored energy of less than or equalto about 15.00 J/m².
 28. The glass pharmaceutical package according toclaim 1, wherein the glass pharmaceutical package comprises a storedenergy of greater than or equal to 17.00 J/m².